Direct Evaluation of Intrinsic Optoelectronic Performance of Organic Photovoltaic Cells with Minimizing Impurity and Degradation Effects

A correlation between the photovoltaic performance and dynamics of transient photoconductivity is investigated by flash‐photolysis time‐resolved microwave conductivity (FP‐TRMC). This electrode‐less technique offers chances to mitigate barriers for direct, speedy, and robust evaluation of bulk heterojunction (BHJ) film. We examined the blend ratio, process (solvent and thermal annealing), and impurity (a metal complex of Pd) and degradation effects in BHJ films consisting of poly(3‐hexylthiophene) (P3HT) and methanofullerene (PCBM). The minimum charge carrier mobility of 0.22 cm²V^?1s^?1 was found in P3HT:PCBM = 1:1 film along with 3.26% power conversion efficiency. The revealed good correlation is not only applicable to process optimization, but also expected as a facile screening method to survey the potential of optoelectronic materials.     

Light-induced conductivity changes in purple membrane suspensions.

Small light-induced changes in the conductivity of light-adapted purple membrane suspended in strong electrolyte solutions were detected. The method used involved modulated light and a phase sensitive detector and it allowed us to detect accurately changes as small as 0.0001% in the conductivity of the suspension. The light-induced conductivity changes turned out to be composed of at least two different event: a small fast increase in conductivity (tau approximately 2 ms) followed by a slower and larger decrease in this parameter (tau = 70 ms-80 ms). The effects of pH and temperature on these changes were studied. Both events reached maximal values around neutral pH and approached zero at both high and low pH's. Heating the suspension decreased the photoconductivity change and Arrhenius plots of the data showed breaks around 31 degrees C. It is suggested that the conductivity changes reflect changes in the surface charge of the membrane and can be used to follow the kinetics of the conformational changes occurring in the system.     

Comparing cardiac action potentials recorded with metal and glass microelectrodes

Machine-pulled high-impedance glass capillary microelectrode is standard for transmembrane potential (TMP) recordings. However, it is fragile and difficult to impale, especially in beating myocardial tissues. We hypothesize that a high-impedance pure iridium metal electrode can be used as an alternative to the glass microelectrode for TMP recording. The TMPs were simultaneously recorded from isolated perfused swine right ventricles with a metal microelectrode and a standard glass microelectrode during pacing and during ventricular fibrillation. The basic morphology of TMP recorded with these electrodes was comparable. The action potential duration (APD) at 90% repolarization was 241 +/- 29 ms for the metal microelectrode and 236 +/- 31 ms for the glass microelectrode with a good correlation (r = 0.99, P < 0.0001). The maximum slope value of the APD restitution curves during pacing was also significantly correlated. One metal microelectrode and >20 glass microelectrodes were needed per study. We conclude that, in isolated perfused swine right ventricles, the TMP recorded by the metal microelectrode is comparable with that recorded by the glass microelectrode. Because the metal microelectrode is more durable than the glass microelectrode, it can serve as an alternative for APD recording and for restitution analyses.     

Photogating of ionic currents across lipid bilayers. Hydrophobic ion conductance by an ion chain mechanism.

The photogating of hydrophobic ion currents across the lipid bilayer membrane allows the direct study of their kinetics by symmetrically forming charge within the membrane and across each interface, rather than across the membrane. We find that the photoinduced conductance continues to increase beyond the region where the tetraphenylboride charge density in the membrane exceeds the estimated porphyrin cation density. This photoconductance is proportional to the tetraphenylboride charge density raised to the second to third power. The risetime of the photogating effect increases with increasing concentration of tetraphenyl boride. The porphyrin cation mobility is increased when the tetraphenylboride anion is present, and low concentrations of tetraphenylphosphonium cation increase the dark conductivity while inhibiting the photoconductivity. The activation energy for both the porphyrin and phosphonium cation induced conductance is more positive than that of the tetraphenylboride conductance. From these results we conclude that in addition to some cancellation of space charge within the membrane, the mechanism of increased conductance involves the transport of these hydrophobic anions via an alternating anion-cation chain, analogous to the Grotthuss mechanism for excess proton conduction in water. This ion chain conductance can be viewed as an evolutionary prototype of an ion channel across the membrane. It also underscores the importance of the counter ion in the transport of large ions such as peptides across the lipid bilayer.     

Light-induced conductivity changes in purple membrane suspensions

Small light-induced changes in the conductivity of light-adapted purple membrane suspended in strong electrolyte solutions were detected. The method used involved modulated light and a phase sensitive detector and it allowed us to detect accurately changes as small as 0.0001% in the conductivity of the suspension. The light-induced conductivity changes turned out to be composed of at least two different events: a small fast increase in conductivity (t ∼ 2 ms) followed by a slower and larger decrease in this parameter (Τ=70 ms-80 ms). The effects of pH and temperature on these changes were studied. Both events reached maximal values around neutral pH and approached zero at both high and low pH's. Heating the suspension decreased the photoconductivity change and Arrhenius plots of the data showed breaks around 31‡ C. It is suggested that the conductivity changes reflect changes in the surface charge of the membrane and can be used to follow the kinetics of the conformational changes occuring in the system.     

Metal particle-enhanced fluorescent immunoassays on metal mirrors

We present fluoroimmunoassays on plain metal-coated surfaces (metal mirrors) enhanced by metal nanoparticles (silver island films [SIFs]). Metal mirrors (aluminum, gold, or silver protected with a thin silica layer) were coated with SIFs, and an immunoassay (model assay for rabbit immunoglobulin G or myoglobin immunoassay) was performed on this surface using fluorescently labeled antibodies. Our results showed that SIFs alone (on glass surface not coated with metal) enhance the immunoassay signal approximately 3- to 10-fold. Using a metal mirror instead of glass as support for SIFs results in up to 50-fold signal enhancement.     

Proton tunneling in hydrated biological tissues near 200 K

We measure the protonic conductivity in water clusters adsorbed on intact samples of viable biological samples (corn embryo and endosperm, Artemia cysts, and Typha pollen) below room temperature. In the low-temperature region, the conductivity increases with temperature as exp T6, in agreement with prediction by the theory of dissipative quantum tunneling. We detect the onset of this effect near 180 K, where a glass transition in the hydrated protein matrix is known to take place. Above 220 K other transitions are superimposed onto this simple behavior.     

Daylight ultraviolet radiation and the photoinhibition of phytoplankton carbon uptake

¹⁴C carbonate uptake by phytoplankton in quartz and laborator4yglass vessels was compared in full daylight. Carbon uptake inthe Laboratory glass vessels was –25% higher during 1.5and 3.7 h incubations. Covering the quartz vessels with 6 rumthick soda-lime glass led to carbon uptake rates 80% higherthan in unshaded quartz bottles. The differences in carbon uptakerates can be explained by the transmittance characteristicsof the different glass types (approximate cut-off wavelengthfor laboratory glass = 320 mm and for soda-lime glass = 350mm). Additional expenrnents yielded preliminary data on theeffective photoinhibiting spectrum in daylight (the productof the action spectrum of photoinhibition and the downwellingspectral irradiance at noon). It is concluded that at Latitudesof central Europe in the summer the donunant photoinhibitionwavelength, during noon hours on a bright day, is between 320nm and 360 nm. ^*This paper is the result of a study made at the Group for AquaticPrimary Productivity (GAP) First International Workshop heldat the Limnological Institute, University of Konstanz, in April1982.     

Semiconductor properties of melanins prepared from catecholamines

D. C. dark - and photoconductivity measurements were performed with synthetic melanins prepared by oxidative polymerization of dopamine, adrenaline, adrenochrome and adrenolutin. The melanins examined show significant differences in conductivity, thermal activation energy and photocurrent intensity values. The differences in semiconductor properties observed between the melanins reflect the structure differences of catecholamine-melanin polymers.     

Rectified photocurrent of molecular photodiode consisting of cytochrome c/GFP hetero thin films.

Photoinduced electron transfer in the molecular electronic device consisting of protein-adsorbed hetero Langmuir–Blodgett (LB) film was investigated. Three kinds of functional molecules, cytochrome c, viologen, and green fluorescent protein (GFP) were used as an electron acceptor, a mediator, and a sensitizer, respectively. The hetero-LB film was fabricated by subsequently depositing cytochrome c and viologen onto the pretreated ITO or quartz glass. GFP adsorbed hetero-LB films were prepared by soaking the hetero-LB films into the buffer solution containing GFP. The MIM (metal/insulator/metal) structured molecular device was constructed by depositing aluminum onto the surface of the GFP-adsorbed hetero LB films. Due to the excitation by irradiation with a 460 nm monochromic light source, the photoinduced unidirectional flow of electrons in the MIM device could be achieved and was detected as photocurrents. The photoswitching function was achieved and the rectifying characteristic was observed in the molecular device. Based on the measurement of transient photocurrent of molecular device, the unidirectional flow of electrons was verified.     

High-throughput RNA extraction from plant samples based on homogenisation by reciprocal shaking in the presence of a mixture of sand and glass beads

We describe here a reliable high-throughput method for extraction of RNA from fresh or frozen plant tissue that obviates laborious and time-consuming homogenisation by mortar and pestle. The method is based on homogenisation by high-speed reciprocal shaking in presence of a mixture of inexpensive abrasive materials; i.e., quartz sand and glass beads. After homogenisation, the method follows a standard procedure for RNA extraction by phenol/LiCl. Yield and quality of RNA obtained by homogenisation with the sand/glass bead mix are identical to those obtained by mortar and pestle.     

Rectified photocurrent of molecular photodiode consisting of cytochrome c/GFP hetero thin films

Photoinduced electron transfer in the molecular electronic device consisting of protein-adsorbed hetero Langmuir–Blodgett (LB) film was investigated. Three kinds of functional molecules, cytochrome c, viologen, and green fluorescent protein (GFP) were used as an electron acceptor, a mediator, and a sensitizer, respectively. The hetero-LB film was fabricated by subsequently depositing cytochrome c and viologen onto the pretreated ITO or quartz glass. GFP adsorbed hetero-LB films were prepared by soaking the hetero-LB films into the buffer solution containing GFP. The MIM (metal/insulator/metal) structured molecular device was constructed by depositing aluminum onto the surface of the GFP-adsorbed hetero LB films. Due to the excitation by irradiation with a 460 nm monochromic light source, the photoinduced unidirectional flow of electrons in the MIM device could be achieved and was detected as photocurrents. The photoswitching function was achieved and the rectifying characteristic was observed in the molecular device. Based on the measurement of transient photocurrent of molecular device, the unidirectional flow of electrons was verified.     

Ordered association of tobacco mosaic virus in the presence of divalent metal ions

The formation of ordered aggregates of tobacco mosaic virus (TMV) in the presence of divalent metal ions has been studied in concentrated (1-25 mg/ml) solutions of the virus. The divalent metal cations Cd2+, Zn2+, Pb2+, Cu2+, and Ni2+ have been found to promote TMV precipitation from solution at a critical concentration Ccrit, which for a given metal depends on the pH and the ionic strength of the solution, but is largely independent of the virus concentration. The TMV precipitate behaves as a nematic liquid crystal and on drying at a glass surface produces highly ordered, optically birefringent films. However, precipitation is not observed with alkali-earth metals such as Ca2+ and Mg2+. The experimental data suggest that, apart from two 'internal' metal-binding sites in each TMV subunit, the virus contains metal-binding sites of a lower affinity which promote cross-linking of TMV rods via metal bridges. The latter seem to be responsible for the precipitation of TMV in the presence of divalent cations at neutral pH. We propose that the metal-induced cross-linking may be the predominant mechanism to account for the limited solubility of a variety of proteins in solution containing metal cations with valence 2 and higher.     

Quantifying the cleanliness of glass capillaries

I used capillary rise methods to investigate the lumenal surface properties of quartz (fused silica, Amersil T-08), borosilicate (Corning 7800), and high-lead glass (Corning 0010) capillaries commonly used to make patch pipets. I calculated the capillary rise and contact angle for water and methanol from weight measurements. The capillary rise was compared with the theoretical maximum value calculated by assuming each fluid perfectly wetted the lumenal surface of the glass (i.e., zero contact angle, which reflects the absence of surface contamination). For borosilicate, high-lead, and quartz capillaries, the rise for water was substantially less than the theoretical maximum rise. Exposure of the borosilicate, lead, and quartz capillaries to several cleaning methods resulted in substantially better—but not perfect—agreement between the theoretical maximum rise and calculated capillary rise. By contrast, the capillary rise for methanol was almost identical in untreated and cleaned capillaries, but less than its theoretical maximum rise. The residual discrepancy between the observed and theoretical rise for water could not be improved on by trying a variety of cleaning procedures, but some cleaning methods were superior to others. The water solubility of the surface contaminants, deduced from the effectiveness of repeated rinsing, was different for each of the three types of capillaries examined: Corning 7800>quartz>Corning 0010. A surface film was also detected in quartz tubing with an internal filament. I conclude that these borosilicate, quartz, and high-lead glass capillaries have a film on the lumenal surface, which can be removed using appropriate cleaning methods. The surface contaminants may be unique to each type of capillary and may also be hydrophobic. Two simple methods are presented to quantitate the cleanliness of glass capillary tubing commonly used to make pipets for studies of biological membranes. It is not known if the surface film is of importance in electrophysiological studies of biological membranes.     

EFFECT OF THE HYDROGEN ION CONCENTRATION ON THE PHAGOCYTOSIS AND ADHESIVENESS OF LEUCOCYTES

1. Immediately after coming into contact with glass, leucocytes are most adhesive at pH 8.0 or > 8.0. 2. Agglutination of leucocytes increases with increasing H ion concentration from pH 8.0 to 6.0. 3. In phagocytosis experiments where leucocytes creep about on the slide picking up articles the optimum pH is 7.0. Here ameboid movement is probably the limiting factor. 4. The optimum for phagocytosis of quartz from suspension is on the acid side of neutrality at or near pH 6.7. 5. Phagocytosis of quartz increases with the acidity, while adhesiveness of leucocytes to glass increases with the alkalinity.     

Recent Developments and Understanding of Novel Mixed Transition‐Metal Oxides as Anodes in Lithium Ion Batteries

Mixed transition‐metal oxides (MTMOs), including stannates, ferrites, cobaltates, and nickelates, have attracted increased attention in the application of high performance lithium‐ion batteries. Compared with traditional metal oxides, MTMOs exhibit enormous potential as electrode materials in lithium‐ion batteries originating from higher reversible capacity, better structural stability, and high electronic conductivity. Recent advancements in the rational design of novel MTMO micro/nanostructures for lithium‐ion battery anodes are summarized and their energy storage mechanism is compared to transition‐metal oxide anodes. In particular, the significant effects of the MTMO morphology, micro/nanostructure, and crystallinity on battery performance are highlighted. Furthermore, the future trends and prospects, as well as potential problems, are presented to further develop advanced MTMO anodes for more promising and large‐scale commercial applications of lithium‐ion batteries.     

Lipid monolayer-coated solid surfaces do not perturb the lateral motion and distribution of C3b receptors on neutrophils

We have used epifluorescence and photobleaching techniques to study the lateral distribution and motion of fluorescein-conjugated Fab fragments of anti-C3b receptor antibody bound to human neutrophils when the cells rest on various solid supports (microscope slides or cover slips). Supports composed of quartz, glass, or alkylated glass induced cellular adhesion, spreading, and an extensive lateral redistribution of C3b receptors (but not HLA antigens). The neutrophil C3b receptors become patchy, and the patches apparently undergo nonrandom translational motion. Many patches are found on the upper surfaces of the cells removed from the region of cell membrane-glass contact. In contrast, neutrophils supported by lipid monolayer-coated glass do not adhere or spread, and the C3b receptor remains uniform and diffuses freely (D approximately equal to 2 X 10(-10) cm2/s).     

Resonance acoustic microbalance with naked-embedded quartz (RAMNE-Q) biosensor fabricated by microelectromechanical-system process

A resonance acoustic microbalance with a naked-embedded quartz (RAMNE-Q) is realized by a microfabrication method, aiming at broader applications of quartz-crystal microbalance (QCM) biosensors. The RAMNE-Q biosensor consists of three layers; a silicon layer with an engraved microchannel and sandwiching glass layers. The naked AT-cut quartz resonator of 9.3 or 28.5 μm thick is located in the microchannel and supported by the silicon micropillars and semicircular walls without fixing, and it is encapsulated by the rigid body. Cupper antennas are used for generating and receiving electromagnetic fields to excite and detect the shear vibration of the quartz oscillator during the solution flow, thereby achieving the noncontact measurement of the resonance frequency. Because of the isolated resonator, the Q factor is high enough (about 1500 at 170-180 MHz) even in the flowing solution. We succeeded in detecting 1 ng/ml human immunoglobulin G in phosphate-buffered-saline solution via Staphylococcus aureus protein A immobilized nonspecifically on the quartz surfaces, demonstrating the high sensitivity and high signal-to-noise ratio of the RAMNE-Q biosensor. It does not require electrodes and is a replacement-free biosensor, and its reusability is confirmed.     

Theoretical electrical conductivity of hydrogen-bonded benzamide-derived molecules and single DNA bases

A benzamide molecule is used as a “reader” molecule to form hydrogen bonds with five single DNA bases, i.e., four normal single DNA bases A,T,C,G and one for 5methylC. The whole molecule is then attached to the gold surface so that a meta-molecule junction is formed. We calculate the transmission function and conductance for the five metal–molecule systems, with the implementation of density functional theory-based non-equilibrium Green function method. Our results show that each DNA base exhibits a unique conductance and most of them are on the pS level. The distinguishable conductance of each DNA base provides a way for the fast sequencing of DNA. We also investigate the dependence of conductivity of such a metal–molecule system on the hydrogen bond length between the “reader” molecule and DNA base, which shows that conductance follows an exponential decay as the hydrogen bond length increases, i.e., the conductivity is highly sensitive to the change in hydrogen bond length.     

Correlation of mitochondria metabolism and spontaneous luminescence of incubation cells

Correlation between metabolism of isolated mitochondria (M) and the energetic state of incubation cells structure was studied. The energetic state was determined by the intensity of spontaneous superlow luminescence (LM). Correlation was found between M respiration rate, oxidative phosphorylation and the incubation cells LM. Variations of M metabolism correlating with the LM level of the cells made of quartz and organic glass are of opposite direction. Independently of LM value of the cells there was found a reliable successive decrease of M respiration rate in the course of their incubation in the quartz cells with a decreased response to stimulation additions (ADP, DHP), and an increase of the time of aerobic phase. A decrease of the rate of oxygen consumption and phosphorylation was observed also in the organic glass cells with a low LM level. The indexes of metabolism in the organic glass cells with a high LM level corresponded to the usual control. An increase of LM level of the whole system (M + medium + incubation + cell) was observed during M incubation in optically low-transparent (organic glass) and untransparent (ebonite) cells. On the contrary when M were incubated in transparent quartz cells a decrease of LM level was observed. Changes of LM and respiration are suggested to be related to the existence of coherent electromagnetic vibrations in the components of the system under study, and with the dependence of the mobility degree of molecular oxygen on the level of structure pattern of the biological systems.