Solution-Deposited Thin Silver Films on Plastic Surfaces for Low-Cost Applications in Plasmon-Coupled Emission Sensors

We report the deposition of highly uniform thin silver films on plastic materials using a wet-chemistry method, suitable for surface plasmon-coupled emission (SPCE). This approach is reproducible for diverse low-cost applications and versatile to generate silver surfaces on various plastics substrates. An oxygen plasma pretreatment of the plastic provides for rapid silvering, leading to a 47-nm-thick continuous film for SPCE applications. The surface smoothness and thickness of the films have been estimated using atomic force microscope. The higher refractive index of polycarbonate, resulted in an SPCE angle of θ _F = 47⁰ for Rhodamine B, compared to glass (θ _F = 50⁰). The current study presents details on film deposition conditions, appropriate choice of index matching fluids, substrates, and light sources that play a vital role to augment SPCE emission intensity.     

The influence of nanoscopically thin silver films on bacterial viability and attachment

The physicochemical and bactericidal properties of thin silver films have been analysed. Silver films of 3 and 150 nm thicknesses were fabricated using a magnetron sputtering thin-film deposition system. X-ray photoelectron and energy dispersive X-ray spectroscopy and atomic force microscopy analyses confirmed that the resulting surfaces were homogeneous, and that silver was the most abundant element present on both surfaces, being 45 and 53 at.% on the 3- and 150-nm films, respectively. Inductively coupled plasma time of flight mass spectroscopy (ICP-TOF-MS) was used to measure the concentration of silver ions released from these films. Concentrations of 0.9 and 5.2 ppb were detected for the 3- and 150-nm films, respectively. The surface wettability of the films remained nearly identical for both film thicknesses, displaying a static water contact angle of 95°, while the surface free energy of the 150-nm film was found to be slightly greater than that of the 3-nm film, being 28.8 and 23.9 mN m⁻¹, respectively. The two silver film thicknesses exhibited statistically significant differences in surface topographic profiles on the nanoscopic scale, with R _a, R _q and R _max values of 1.4, 1.8 and 15.4 nm for the 3-nm film and 0.8, 1.2 and 10.7 nm for the 150-nm film over a 5 × 5 μm scanning area. Confocal scanning laser microscopy and scanning electron microscopy revealed that the bactericidal activity of the 3-nm silver film was not significant, whereas the nanoscopically smoother 150-nm silver film exhibited appreciable bactericidal activity towards Pseudomonas aeruginosa ATCC 9027 cells and Staphylococcus aureus CIP 65.8 cells, obtaining up to 75% and 27% sterilisation effect, respectively.     

Surface Plasmon Dynamics of High-Aspect-Ratio Gold Nanorods

Ultrafast transient absorption studies are reported for high-aspect-ratio gold nanorods that were fabricated by electrochemical deposition in polycarbonate templates. The nanorods are 60 nm in diameter with distribution of lengths of up to 6 μm. The average aspect ratio was ∼50, resulting in a longitudinal surface plasmon resonance (SPR_L) band in the mid-IR, as well as a transverse (SPR_T) band in the visible. The rods were excited at 400 nm and probed at a range of wavelengths from the visible to the mid-IR to interrogate both SPR bands. The dynamics observed, including the electron–phonon coupling time and coherent acoustic breathing mode oscillations, closely resemble those previously reported for gold spherical nanoparticles and smaller-aspect-ratio nanorods. The electron–phonon coupling time was similarly determined to be 3.3 ± 0.2 ps for both of the SPR bands. Also, oscillations with a 32-ps period were observed for probing near the SPR_T band in the visible region due to impulsive coherent excitation of the acoustic breathing mode, which are consistent with the 60-nm diameter of the nanorods determined by scanning electron microscopy. The results demonstrate that the dynamics for long gold nanorods are similar to those for smaller nanoparticles. Gerald M. Sando is a NRL-ASEE Research Associate     

In situ separation of root hydraulic redistribution of soil water from liquid and vapor transport

Nocturnal increases in water potential (ψ) and water content (θ) in the upper soil profile are often attributed to root water efflux, a process termed hydraulic redistribution (HR). However, unsaturated liquid or vapor flux of water between soil layers independent of roots also contributes to the daily recovery in θ (Δθ), confounding efforts to determine the actual magnitude of HR. We estimated liquid (J _l) and vapor (J _v) soil water fluxes and their impacts on quantifying HR in a seasonally dry ponderosa pine (Pinus ponderosa) forest by applying existing datasets of ψ, θ and temperature (T) to soil water transport equations. As soil drying progressed, unsaturated hydraulic conductivity declined rapidly such that J _l was irrelevant (<2E−05 mm h⁻¹ at 0–60 cm depths) to total water flux by early August. Vapor flux was estimated to be the highest in upper soil (0–15 cm), driven by large T fluctuations, and confounded the role of HR, if any, in nocturnal θ dynamics. Within the 15–35 cm layer, J _v contributed up to 40% of hourly increases in nocturnal soil moisture. While both HR and net soil water flux between adjacent layers contribute to θ in the 15–65 cm soil layer, HR was the dominant process and accounted for at least 80% of the daily recovery in θ. The absolute magnitude of HR is not easily quantified, yet total diurnal fluctuations in upper soil water content can be quantified and modeled, and remain highly applicable for establishing the magnitude and temporal dynamics of total ecosystem water flux.     

Citrate Uptake into Tonoplast Vesicles from Acid Lime (Citrus aurantifolia) Juice Cells

Citrate transport into the vacuoles of acid lime juice cells was investigated using isolated tonoplast vesicles. ATP stimulated citrate uptake in the presence or in the absence of a ΔμH⁺. Energization of the vesicles only by an artificial K⁺ gradient (establishing an inside-positive Δψ) also resulted in citrate uptake as was the case of a ΔpH dominated ΔμH⁺. Addition of inhibitors to endomembrane ATPases showed no direct correlation between the inhibition to the tonoplast bound H⁺/ATPase and citrate uptake. The data indicated that, although some citrate uptake can be accounted for by Δψ and by a direct primary active transport mechanism involving ATP, under in vivo conditions of vacuolar pH of 2.0, citrate uptake is driven by ΔpH. Received: 27 April 1998/Revised: 8 September 1998     

Thin liquid films and monolayers of DMPC mixed with PEG and phospholipid linked PEG

In this work thin liquid films (TLFs) and monolayers at the air/water interface formed by dimyristoylphosphatidylcholine (DMPC) and by DMPC mixed with poly ethylene glycols (PEGs) and dimyristoylphosphatidylethanolamine (DMPE) linked PEGs were studied. Film forming dispersions were composed of two types of particles: liposomes and micelles. TLFs stability, threshold concentration C _t (i.e., the minimum one for stable film formation), and hydrodynamic behavior were measured. At equivalent conditions, DMPC films were Newton black films (real bilayers), while DMPE-PEGs films were much thicker with free water between the monolayers. DMPE-PEG addition to DMPC films caused both C _t decrease (depending on PEG moiety length and Mw) and change of TLF formation mechanism. TLFs’ hydrodynamic behavior also strongly depended on DMPE-PEG content and Mw. It was observed that thinning of the DMPC and DMPE-PEGs films continued to different film types and thickness, being much thicker for the latter films. Addition of free PEGs (PEG-200/6000) did not alter TLF type or stability, but changed TLF thinning time, confirming that free PEGs with Mw<8000 could not penetrate in the membrane and alter “near-membrane” water layer viscosity. Monolayer studies showed improved formation kinetics of both adsorbed and spread films, decrease of surface tension (equilibrium and dynamic), and of film compression/decompression histeresis area in DMPE-PEGs monolayers compared with DMPC pure films. Our study shows that combining the models of phospholipid TLFs and monolayers provide the opportunity to investigate the properties of membrane surface and to clarify some mechanisms of its interactions with membrane-active agents.     

Surface plasmon resonance imaging analysis of hexahistidine-tagged protein on the gold thin film coated with a calix crown derivative

A surface plasmon resonance (SPR) imaging system was constructed and used to detect the hexahistidine-ubiquitin-tagged human parathyroid hormone fragment (His₆-Ub-hPTHF(1–34)) expressed inEscherichia coli. The hexahistidine-specific antibody was immobilized on a thin gold film coated with ProLinker^TM B, a novel calixcrown derivative with a bifunctional coupling property that permits efficient immobilization of capture proteins on solid matrices. The soluble and insoluble fractions of anE. coli cell lysate were spotted onto the antibody-coated gold chip, which was then washed with buffer (pH 7.4) solution and dried. SPR imaging measurements were carried out to detect the expressed His₆-Ub-hPTHF (1–34). There was no discernible protein image in the uninduced cell lysate, indicating that non-specific binding of contaminant proteins did not occur on the gold chip surface. It is expected that the approach used here to detect affinity-tagged recombinant proteins using an SPR imaging technique could be used as a powerful tool for the analyses of a number of proteins in a high-throughput mode.     

The application of sterol biomarkers to the study of the sources of particulate organic matter in the Solo River system and and Serayu River,Java, Indonesia

Sterols were analyzed in suspended particles collected in January 1991 in the Solo River system and in the Serayu River, Java, Indonesia. Free sterols were extracted from particles larger than 0.7 μm and analyzed, after derivatization into their trimethylsilyl esters, by GC and GC/MS. Concentrations of total sterols ranged from 438 to 7922 ng/1, or from 2.4 to 183.8 ng/mg of total suspended matter, which varied from 3.3 to 400 and 471 mg/l, respectively in the Serayu River and at the downstream station in the Solo River. POC concentrations also varied in a wide range, from 0.91 to 4.72 and 6.13% of TSM, respectively at the above stations, and were associated with sterol/POC values ranging from 0.15 to 1.75 μg/mg. Eleven structures of C₂₇, C₂₈ and C₂₉ sterols and associated stanols were identified. 28Δ^3,22 was only found at downstream stations in the Solo River and in the Serayu River. This unique distribution, different from that of other C₂₇, C₂₈ and C₂₉ sterols, suggests a predominantly autochthonous origin for these compounds associated with an increased planktonic biosynthesis near the estuary. Concentrations of 28Δ⁵, 29Δ^5,22 and 29Δ⁵ showed similar spatial distributions and increased downstream, reflecting the significant accumulation of organic matter originating from the vegetation of the various drainage basins. Values of the autochthonous versus terrigenous sterol index, defined as 27Δ⁵/29Δ^5,22 + 29Δ⁵ were in the 1.4–1.9 range at upstream stations, whereas at downstream stations lower values were found, 0.4–0.6, which also corresponded to higher concentrations of TSM and lower POC values. Insofar as the stanol/stenol values can be used to estimate the bacterial activity of oxic waters, simultaneous variations of C₂₇, and C₂₉ stenol/stanol pairs suggest rather different bacterial degradation capacities of autochthonous versus allochthonous organic matter. The wide differencies between the values of the stenol/stanol pairs observed in one of the main tributaries and in downstream stations of the Solo River is evidence that allochthonous organic matter is much more resistant than autochthonous matter. The low index value observed in the Serayu River indicates the highly refractory nature of both autochthonous and allochthonous organic material.     

Glutathione peroxidase3 of <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis> protects phospholipids during cadmium-induced oxidative stress

The present study was undertaken to determine the role of glutathione peroxidase3 (gpx3) in phospholipid protection in cells. Wild-type (WT) cells showed an overall increase in phospholipids upon 50 μM cadmium (Cd)-treatment, whereas an untreated gpx3Δ strain showed a drastic reduction in overall phospholipids which was further reduced with 50 μM Cd. In WT cells, Cd-exposure increased the short chain fatty acids and decreased the unsaturated fatty acids and the magnitude was high in Cd-treated gpx3Δ cells. Purified recombinant gpx3p showed higher activity with phospholipid hydroperoxides than shorter hydroperoxides. An increase in gpx activity was observed in Cd-treated WT cells and no such alteration was observed in gpx3Δ. WT cells treated with Cd showed an increase in MDA over untreated, while untreated gpx3Δ cells themselves showed a higher level of MDA which was further enhanced with Cd-treatment. Iron, zinc and calcium levels were significantly altered in WT and gpx3Δ cells during Cd-treatment.     

Respiratory and metabolic responses of the Australian Yabby Cherax destructor to progressive and sustained environmental hypoxia

The Australian Yabby, Cherax destructor, inhabits occasionally hypoxic water. The respiratory gas, acid-base, metabolite and energetic status of this crayfish was assessed during progressive hypoxia and during 3 h at a water PO₂ of 1.33 kPa. The O₂ affinity of haemocyanin from C. destructor was increased by lactate (Δlog P ₅₀/Δlog[lactate] = −0.111) and by Ca (Δlog P ₅₀/Δlog[Ca] = −0.62) but not by urate. While the non-bicarbonate buffering capacity was low (Δ[HCO₃ ⁻]/ ΔpH=−4.89) the haemocyanin had a low sensitivity to pH changes (ϕ = −0.33). The crayfish showed a compensatory hyperventilation, which induced a respiratory alkalosis, until the water O₂ partial pressure declined below 2.67 kPa, after which the O₂ uptake rate was approximately 10% of normoxic rates. The high haemocyanin-O₂ affinity maintained haemolymph O₂ content during progressive hypoxia despite the normally low arterial O₂ partial pressure of C. destructor. During severe hypoxia, pH decreased but increased lactate aided in maintaining haemocyanin-O₂ saturation. The importance of regulated haemocyanin-O₂ affinity in hypoxic C. destructor was reduced by lowered metabolism, including reduced cardiac output, and the consequent reduction in O₂ requirement. Anaerobiosis became important only at very low PO₂ but thereafter proceeded rapidly, supported by a marked hyperglycaemia. There was no depletion of adenylates, even after 3 h of severe hypoxia. The tail muscle of C. destructor held small amounts of glycogen which would sustain anaerobiosis for a only a few hours. Hypometabolism seems an important hypoxic response but severe hypoxia may encourage the crayfish to breathe air. Accepted: 26 February 1998     

Molecular mechanism for the initial process of visual excitation. IV. Energy surfaces of visual pigments and photoisomerization mechanism

Using the twisted conformations of the chromophores for visual pigments and intermediates which were theoretically determined in the previous paper, energy surfaces of the pigment at −190‡ C were obtained as functions of the torsional anglesθ _9–10 andθ _11–12 or of the torsional anglesθ _9–10 andθ _13–14. In these calculations, the existence of specific reaction paths between rhodopsin (R) and bathorhodopsin (B), between isorhodopsin I (I) and bathorhodopsin, and between isorhodopsin II (I′) and bathorhodopsin were assumed. It was shown that the total energy surfaces of the excited states had minimaC ₁ atθ _9–10 ∼ −10‡ andθ _11–12 ∼ −80‡,C ₂ atθ _9–10 ∼ −85‡ andθ _11–12 ∼ −5‡, andC ₃ atθ _9–10 ∼ 0‡ andθ _13–14 ∼ −90‡. These minima are considered to correspond to the thermally barrierless common states as denoted by Rosenfeld et al. Using the total energy surfaces in the ground and excited states, the molecular mechanism of the photoisomerization reaction was suggested. Quantum yields for the photoconversions among R, I, I′ and B were related to the rates of vibrational relaxations, radiationless transitions and thermal excitations. Some discussion was made of the temperature effect on the quantum yield. Similar calculations of the energy surfaces were also made at other temperatures where lumirhodopsin or metarhodopsin I is stable. Relative energy levels of the pigments and the intermediates were discussed.     

Surface Rheology Parameters of Source-Specific Surfactant Films as Indicators of Organic Matter Dynamics

The paper contains the results of natural film experiments carried out on inland and coastal waters in the Dead Vistula catchment area and mouth during 2000–2002, using the integrated Langmuir trough–Wilhelmy plate system. The static film parameters result from the generalized scaling procedures applied to the surface pressure–area isotherms. They appear to reflect in a quantitative and sensitive way the film composition (A_lim, M_w, E_isoth), film solubility and the miscibility of its components (via R, ΔS_c and y factors), and surface concentration (π_eq, Γ_eq). The adsorption kinetics parameters: effective diffusion coefficient D_eff/D and activation energy barrier E_a/RT are derived from dynamic surface pressure. There is a reason to suggest that certain classes of film-forming components or ‘end-members’ may dominate the static and dynamic surface properties. Variation in the surface rheological parameters of source-specific biosurfactants is postulated to reflect organic matter dynamics in natural waters and were measured for the Dead Vistula river, its tributaries and the adjacent coastal area.     

Plasmonic and Nonlinear Optical Absorption Properties of Ag:ZrO2 Nanocomposite Thin Films

Ag nanoparticles (NPs) embedded in a zirconium oxide matrix in the form of Ag:ZrO₂ nanocomposite (NC) thin films were synthesized by using the sol–gel technique followed by thermal annealing. With the varying of the concentration of Ag precursor and annealing conditions, average sizes (diameters) of Ag nanoparticles (NPs) in the nanocomposite film have been varied from 7 to 20 nm. UV–VIS absorption studies reveal the surface plasmon resonance (SPR)-induced absorption in the visible region, and the SPR peak intensity increases with the increasing of the Ag precursor as well as with the annealing duration. A red shift in SPR peak position with the increase in the Ag precursor concentration confirms the growth of Ag NPs. Surface topographies of these NC films showed that deposited films are dense, uniform, and intact during the variation in annealing conditions. The magnitude and sign of absorptive nonlinearities were measured near the SPR of the Ag NPs with an open-aperture z-scan technique using a nanosecond-pulsed laser. Saturable optical absorption in NC films was identified having saturation intensities in the order of 10¹² W/m². Such values of saturation intensities with the possibility of size-dependent tuning could enable these NC films to be used in nanophotonic applications.     

Phenological influences on the albedo of prairie grassland and crop fields

 The albedo of land surfaces is strongly affected by transient surface conditions. For a vegetated surface, albedo can change with soil moisture, fractional canopy cover, and plant phenology as well as solar zenith angle (θ_s). In this study, the relationships between albedo and plant phenology in prairie grassland and agricultural crops were examined by removing the effect of variations in θ_s. Albedos were evaluated at a constant θ_s, which was assigned to be 20° in this study. For days with a minimum θ_s larger than 20°, a polynomial function that relates albedos to θ_s was derived and applied to estimate the albedos at 20°. After the removal of θ_s variations, the observed albedos of grassland at the Konza Prairie showed a linearly decreasing trend from spring to winter due to prairie phenology. The observed albedo of a maize field showed a clear increase from seedling to peak green stage, except when drought caused a decrease in near-infrared reflectance. The observed albedos of a winter wheat field showed an uninterrupted decrease from peak green to harvesting stage. Received: 30 May 1998 / Accepted 15 July1998     

Mechanosensitive ion channels in chara: influence of water channel inhibitors, HgCl2 and ZnCl2, on generation of receptor potential

Characean internodal cells generate receptor potential (ΔE _m) in response to mechanical stimuli. Upon a long-lasting stimulus, the cells generated ΔE _m at the moment of both compression and decompression, and the amplitude of ΔE _m at the moment of decompression, (ΔE _m)_E, was larger than that at compression. The long-lasting stimulus caused a membrane deformation (ΔD _m) having two components, a rapid one, (ΔD _m)_rapid, at the moment of compression and a slower one, (ΔD _m)_slow, during the long-lasting compression. We assumed that (ΔD _m)_slow might have some causal relation with the larger ΔE _m at (ΔE _m)_E. We treated internodal cells with either HgCl₂ or ZnCl₂, water channel inhibitors, to decrease (ΔD _m)_slow. Both inhibitors attenuated (ΔD _m)_slow during compression. Cells treated with HgCl₂ generated smaller (ΔE _m)_E compared to nontreated cells. On the other hand, cells treated with ZnCl₂ never attenuated (ΔE _m)_E but, rather, amplified it. Thus, the amplitude of (ΔD _m)_slow did not always show tight correlation with the amplitude of (ΔE _m)_E. Furthermore, when a constant deformation was applied to an internodal cell in a medium with higher or lower osmotic value, a cell having higher turgor always showed a larger (ΔE _m)_E. Thus, we concluded that changes in tension at the membrane may be the most important factor to induce activation of mechanosensitive Ca²⁺ channel.     

Improved ethanol production by glycerol-3-phosphate dehydrogenase mutants of Saccharomyces cerevisiae

The anaerobic performance of gpd1Δ and gpd2Δ mutants of Saccharomyces cerevisiae was characterized and compared to that of a wild-type strain under well-controlled conditions by using a high-performance bioreactor. There was a 40% reduction in glycerol level in the gpd2Δ mutant compared to the wild-type. Also the gpd1Δ mutant showed a slight decrease in glycerol formation but to a much lesser degree. As a consequence, ethanol formation in the gpd2Δ mutant was elevated by 13%. In terms of growth, the gpd1Δ mutant and the wild-type were indistinguishable. The gpd2Δ mutant, on the other hand, displayed an extended lag phase as well as a reduced growth rate under the exponential phase. Even though glycerol-3-phosphate dehydrogenase 2 (GPD2) is the important enzyme under anaerobic conditions it can, at least in part, be substituted by GPD1. This was indicated by the higher expression level of GPD1 in the gpd2Δ mutant compared to the wild type. These results also show that the cells are able to cope and maintain redox balance under anaerobic conditions even if glycerol formation is substantially reduced, as observed in the gpd2Δ mutant. One obvious way of solving the redox problem would be to make a biomass containing less protein, since most of the excess NADH originates from amino acid biosynthesis. However, the gpd2Δ mutant did not show any decrease in the protein content of the biomass. Received: 16 February 1998 / Received revision: 16 March 1998 / Accepted: 1 June 1998     

Modulation of Main Lobe for Superfocusing Using Subwavelength Metallic Heterostructures

A subwavelength metallic heterostructure is put forth for the purpose of suppressing sidelobes and improving superfocusing at a quasi-far field region. Improvement has been made by means of optimization of the heterostructure composed of structured Au and Ag thin films. By tuning thicknesses of both the structured Au and Ag films, we can modulate propagation distance of the plasmonic lens and beam width of main lobe for the superfocusing. A finite-difference and time-domain (FDTD) algorithm-based computational numerical calculation was carried out for analyzing the focusing performance and tuning ability of the metal films. Our computational calculation results show that the sidelobes which play negative role for the focusing can be suppressed significantly in the case of the metal film thicknesses of h _Au = 50 nm and h _Ag = 10 nm. Theoretically, the metallic structure with smaller thicknesses of the structured Au and Ag films is helpful for improving the focusing performance. This heterostructure-based device is possible to be used as a superlens or nanoprobe in data storage, nanometrology/inspection, and biosensing etc.     

Gratuitous dechlorination of chloroethanes by methanogenic granular sludge

The dechlorinating activity of a methanogenic granular sludge from a methanol-fed upflow anaerobic sludge blanket reactor was investigated with chlorinated ethanes. This unadapted methanogenic consortium degraded all chloroethanes tested. The product formation rates decreased with the number of chlorine substituents. The more highly chlorinated ethanes were also converted, although at a lower rate, in the presence of autoclaved (dead) sludge, indicating the involvement of reduced heat-stable cofactors like vitamin B₁₂ and F₄₃₀. Direct chemical dechlorination of hexa-, penta- and tetrachloroethanes was also observed in medium without sludge, although at a much lower rate. The results show the importance of cometabolic and abiotic (chemical) conversions for the transformation of chlorinated ethanes by the methanogenic consortium. The types of reaction and the products formed were correlated with the Gibbs free-energy change (ΔG ^0′). Reductive hydrogenolysis and dichloroelimination were important dechlorinating mechanisms. Generally, these reactions have a higher ΔG ^0′ value than dehydrochlorination reactions, which occurred less frequently during the transformation of chloroethanes by the methanogenic granular sludge. Received: 8 June 1998 / Received revision: 7 September 1998 / Accepted: 13 September 1998     

Applications of the ETS-NOCV method in descriptions of chemical reactions

The present study characterizes changes in the electronic structure of reactants during chemical reactions based on the combined charge and energy decomposition scheme, ETS-NOCV (extended transition state–natural orbitals for chemical valence). Decomposition of the activation barrier, ΔE ^#, into stabilizing (orbital interaction, ΔE _orb, and electrostatic, ΔE _elstat) and destabilizing (Pauli repulsion, ΔE _Pauli, and geometry distortion energy, ΔE _dist) factors is discussed in detail for the following reactions: (I) hydrogen cyanide to hydrogen isocyanide, HCN → CNH isomerization; (II) Diels-Alder cycloaddition of ethene to 1,3-butadiene; and two catalytic processes, i.e., (III) insertion of ethylene into the metal-alkyl bond using half-titanocene with phenyl-phenoxy ligand catalyst; and (IV) B–H bond activation catalyzed by an Ir-containing catalyst. Various reference states for fragments were applied in ETS-NOCV analysis. We found that NOCV-based deformation densities (Δρ _i) and the corresponding energies ΔE _orb(i) obtained from the ETS-NOCV scheme provide a very useful picture, both qualitatively and quantitatively, of electronic density reorganization along the considered reaction pathways. Decomposition of the barrier ΔE^# into stabilizing and destabilizing contributions allowed us to conclude that the main factor responsible for the existence of positive values of ΔE ^# for all processes (I, II, III and IV) is Pauli interaction, which is the origin of steric repulsion. In addition, in the case of reactions II, III and IV, a significant degree of structural deformation of the reactants, as measured by the geometry distortion energy, plays an important role. Depending on the reaction type, stabilization of the transition state (relatively to the reactants) originating either from the orbital interaction term or from electrostatic attraction can be of vital importance. Finally, use of the ETS-NOCV method to describe catalytic reactions allows extraction of information on the role of catalysts in determination of ΔE ^#.     

Estimation of seasonal changes in translocation rates in leaves of a Japanese larch stand

To estimate the net rate of translocation in leaves of a larch stand, a new approach based on the summation method was proposed and given by a compartment model. The difference between the rate of translocation into and out of leaf biomass, namely, the net translocation rate (ΔT _r /Δt), was usually expressed by the difference between the growth rate of leaf biomass and the surplus production rate provided that the rate of leaf loss due to leaffall and grazing can be considered negligible. The rate, ΔT _r /Δt in a 19-yr-old larch stand, showed characteristic changes; it was positive from early April to late May, but after that it was negative until leaffall in late October. Our results confirmed that for the growth phase of positive ΔT _r /Δt translocation of assimilate stored in non-photosynthetic organs was indispensable for the growth. To quantify this, the ratio of ΔT _r /Δt to growth rate of leaf biomass was proposed.