Photochemical electron transfer at fixed distance : a synthetic model of the photosynthetic primary process

A series of meso-phenyloctamethylporphyrins covalently bonded at the 4'phenyl position to quinones via rigid bicyclo[2.2.2]octane spacers were synthesized for the study of the dependence of electron transfer reaction rate on solvent, distance, temperature, and energy gap. A general and convergent synthesis was developed based on the condensation of ac-biladienes with masked quinonespacer-benzaldehydes. From picosecond fluorescence spectroscopy emission lifetimes were measured in seven solvents of varying polarity. Rate constants were determined to vary from 5.0x10⁹sec^-1 in N,N-dimethylformamide to 1.15x10¹⁰ Sec^-1 in benzene, and were observed to rise at most by about a factor of three with decreasing solvent polarity. Experiments at low temperature in 2-MTHF glass (77K) revealed fast, nearly temperature-independent electron transfer characterized by non-exponential fluorescence decays, in contrast to monophasic behavior in fluid solution at 298K. This example evidently represents the first photosynthetic model system not based on proteins to display nearly temperature-independent electron transfer at high temperatures (nuclear tunneling). Low temperatures appear to freeze out the rotational motion of the chromophores, and the observed nonexponential fluorescence decays may be explained as a result of electron transfer from an ensemble of rotational conformations. The nonexponentiality demonstrates the sensitivity of the electron transfer rate to the precise magnitude of the electronic matrix element, which supports the expectation that electron transfer is nonadiabatic in this system. The addition of a second bicyclooctane moiety (15 Å vs. 18 Å edge-to-edge between porphyrin and quinone) reduces the transfer rate by at least a factor of 500-1500. Porphyrinquinones with variously substituted quinones allowed an examination of the dependence of the electron transfer rate constant κ_ET on reaction driving force. The classical trend of increasing rate versus increasing exothermicity occurs from 0.7 eV≤ |ΔG^0'(R)| ≤ 1.0 eV until a maximum is reached (κ_ET = 3 x 10⁸ sec^-1 rising to 1.15 x 10¹⁰ sec^-1 in acetonitrile). The rate remains insensitive to ΔG⁰ for ~ 300 mV from 1.0 eV≤ |ΔG^0’(R)| ≤ 1.3 eV, and then slightly decreases in the most exothermic case studied (cyanoquinone, κ_ET = 5 x 10⁹ sec^-1).

Structural and optical properties of a-plane ZnO thin films synthesized on γ-LiAlO2 (302) substrates by low pressure metal-organic chemical vapor deposition

Nonpolar a-plane (1120) ZnO thin films have been fabricated on gamma-LiAlO2 (302) substrates via the low-pressure metal-organic chemical vapor deposition. An obvious intensity variation of the E-2 mode in the Raman spectra indicates that there exhibits in-plane optical anisotropy in the a-plane ZnO thin films. Highly-oriented uniform grains of rectangular shape can be seen from the atomic force microscopy images, which mean that the lateral growth rate of the thin films is also anisotropic. It is demonstrated experimentally that a buffer layer deposited at a low temperature (200 degrees C) can improve the structural and optical properties of the epilayer to a large extent. (c) 2007 Elsevier B.V. All rights reserved.

Role of transglutaminase-mediated cross-linking of protein in the temperature-dependent setting of Alaska pollack surimi

During the low temperature setting of fish paste, myosin heavy chain (MHC) is polymerized to cross-linked myosin heavy chain (CMHC), which is considered to occur by the action of endogenous transglutaminase (TGase). In this study the contribution of TGase on the setting of Alaska pollack surimi at different temperatures was studied. Alaska pollack surimi was ground with 3% NaCl, 30% h2o and with or without ethylene glycol bis (β-aminoethylether) N, N, N¹,N¹- tetra acetic acid (EGTA), an inhibitor of TGase. Among the pastes without EGTA, highest TGase activity was observed at 25°C but breaking force of the gel set at 25°C was lower than that set at 30°, 35°, and 40°C. Addition of EGTA (5m mol/kg) to the paste suppressed TGase activity at all setting temperatures from 20° to 40°C. Gelation of the pastes and cross-linking of MHC on addition of EGTA were suppressed completely at 20° and 25°C, partially at 30° and 35°C, and not at all at 40°C. The findings suggested that during the setting of Alaska pollack surimi TGase mediated cross-linking of MHC was strong at around 25°C but the thermal aggregation of MHC by non-covalent bonds was strong at above 35°C. Setting of surimi at 40°C and cross-linking of its MHC did not involve TGase.

Microbiological quality study of Macrobrachium rosenbergii (de Man 1879) during storage at -20°C temperature

The shelf life of fresh water prawn Macrobrachium rosenbergii by applying low temperature was investigated. M. rosenbergii preserved at -20°C was subjected for quality assessment before storage and at 15, 30, 45, and 90 days of storage period. The quality assessments as done microbiological viz. total bacterial count (TBC), total mould count (TMC), total yeast count (TYC), total coliform count (TCC) and salmonella count. All the samples were acceptable during 90 days because the upper limit of all spoilage indicator was not exceeding within the experimental time period.

Seasonal variations in the activity budget of Nomascus concolor jingdongensis at Mt. Wuliang, Central Yunnan, China: Effects of diet and temperature

We studied seasonal variation in the activity budget of a habituated group of Nomascus concolor jingdongensis at Mt. Wuliang, Central Yunnan, China from March 2005 to April 2006 via scan sampling at 5-min intervals. The study site is near the northern extreme of the distribution of hylobatids, at high altitude with extreme seasonality of temperature and rainfall. During the day, feeding manifested a bimodal pattern of high activity levels in mid-morning and mid-afternoon, whereas resting reached a peak at midday, with proportionally less time used for traveling. Annually, the group spent an average of 40.0% of the time resting, 35.1% feeding, 19.9% traveling, 2.6% singing, 1.2% playing, and 1.3% in other activities. The proportion of time allocated to activities showed significant monthly variations and was influenced by the diet and temperature. Gibbons increased traveling and playing time and decreased feeding time when they ate more fruit, and they decreased traveling, singing, and playing time and increased feeding time when they ate more leaves. Moreover, when the temperature was low, the gibbons decreased time traveling and increased time resting. In summary, black-crested gibbons employed high-effort activities when they ate more fruit and energy-conservation patterns when they ate more leaves and in low temperature. Behavioral data from the site are particularly useful in understanding gibbon behavioral adaptations to different sets of ecological conditions.

Kinetic control of catalytic CVD for high-quality graphene at low temperatures.

Low-temperature (∼600 °C), scalable chemical vapor deposition of high-quality, uniform monolayer graphene is demonstrated with a mapped Raman 2D/G ratio of >3.2, D/G ratio ≤0.08, and carrier mobilities of ≥3000 cm(2) V(-1) s(-1) on SiO(2) support. A kinetic growth model for graphene CVD based on flux balances is established, which is well supported by a systematic study of Ni-based polycrystalline catalysts. A finite carbon solubility of the catalyst is thereby a key advantage, as it allows the catalyst bulk to act as a mediating carbon sink while optimized graphene growth occurs by only locally saturating the catalyst surface with carbon. This also enables a route to the controlled formation of Bernal stacked bi- and few-layered graphene. The model is relevant to all catalyst materials and can readily serve as a general process rationale for optimized graphene CVD.

Complex chemistry DNS of n-heptane spray autoignition at high pressure and intermediate temperature conditions

Direct Numerical Simulations (DNS) of turbulent n-heptane sprays autoigniting at high pressure (P=24bar) and intermediate air temperature (Tair=1000K) have been performed to investigate the physical mechanisms present under conditions where low-temperature chemistry is expected to be important. The initial turbulence in the carrier gas, the global equivalence ratio in the spray region, and the initial droplet size distribution of the spray were varied. Results show that spray ignition exhibits a spotty nature, with several kernels developing independently in those regions where the mixture fraction is close to its most reactive value ξMR (as determined from homogeneous reactor calculations) and the scalar dissipation rate is low. Turbulence reduces the ignition delay time as it promotes mixing between air and the fuel vapor, eventually resulting in lower values of scalar dissipation. High values of the global equivalence ratio are responsible for a larger number of ignition kernels, due to the higher probability of finding regions where ξ=ξMR. Spray polydispersity results in the occurrence of ignition over a wider range of mixture fraction values. This is a consequence of the inhomogeneities in the mixing field that characterize these sprays, where poorly mixed rich spots are seen to alternate with leaner ones which are well-mixed. The DNS simulations presented in this work have also been used to assess the applicability of the Conditional Moment Closure (CMC) method to the simulation of spray combustion. CMC is found to be a valid method for capturing spray autoignition, although care should be taken in the modelling of the unclosed terms appearing in the CMC equations. © 2013 The Combustion Institute.

Temperature dependence of photoluminescence from single core-shell GaAs-AlGaAs nanowires

Temperature-dependent polarized microphotoluminescence measurements of single GaAsAlGaAs core-shell nanowires are used to probe their electronic states. The low-temperature emission from these wires is strongly enhanced compared with that observed in bare GaAs nanowires and is strongly polarized, reflecting the dielectric mismatch between the nanowire and the surrounding air. The temperature-dependent band gap of the nanowires is seen to be somewhat different from that observed in bulk GaAs, and the PL rapidly quenches above 120 K, with an activation energy of 17 meV reflecting the presence of nonradiative defects. © 2006 American Institute of Physics.

Effects of temperature and light on the growth and geosmin production of Lyngbya kuetzingii (Cyanophyta)

The effects of temperature and light on the growth and geosmin production of Lyngbya kuetzingii were determined. Of the three temperatures tested, 10, 25 and 35A degrees C, the maximal geosmin concentration and geosmin productivity were yielded at 10A degrees C, while the highest chl a production was observed at 25A degrees C. In the studies on light intensity, the maximal geosmin concentration and geosmin productivity were observed at 10 mu mol m(-2) s(-1), while the highest chl a production was at 20 mu mol m(-2) s(-1). It was suggested that more geosmin was synthesized with lower chl a demand. Meanwhile, the relative amounts of extra- and intracellular geosmin were investigated. Under optimum growth conditions (20 mu mol m(-2) s(-1), 25A degrees C; BG-11 medium), the amounts of extracellular geosmin increased as the growth progressed and reached the maximum in the stationary phase, while the intracellular geosmin reached its maximum value in the late exponential phase, and then began to decline. However, under the low temperature (10A degrees C) or light (10 mu mol m(-2) s(-1)) conditions, more intracellular geosmin was synthesized and mainly accumulated in the cells. The proportions of extracellular geosmin were high, to 33.33 and 32.27%, respectively, during the stationary phase at 35A degrees C and 20 mu mol m(-2) s(-1). It was indicated that low temperature or light could stimulate geosmin production and favor the accumulation of geosmin in cells, while more intracellular geosmin may be released into the medium at higher temperatures or optimum light intensity.

Temperature dependence of hole spin relaxation in ultrathin InAs monolayers

The temperature dependence of hole spin relaxation time in both neutral and n-doped ultrathin InAs monolayers has been investigated. It has been suggested that D'yakonov-Perel (DP) mechanism dominates the spin relaxation process at both low and high temperature regimes. The appearance of a peak in temperature dependent spin relaxation time reveals the important contribution of Coulomb scatterings between carriers to the spin kinetics at low temperature, though electron-phonon scattering becomes dominant at higher temperatures. Increased electron screening effect in the n-doped sample has been suggested to account for the shortened spin relaxation time compared with the undoped one. The results suggest that hole spins are also promising for building solid-state qubits.

Fiber Bragg grating pressure sensor with ultrahigh sensitivity and reduced temperature sensitivity

A fiber Bragg grating (FBG) pressure sensing scheme based on a flat diaphragm and an L-shaped lever is presented. An L-shaped lever transfers the pressure-induced defection of the flat diaphragm to the axial elongation of the FBG. The curve where the L-shaped lever contacts the diaphragm is a segment of an Archimedes spiral, which is used to enhance the responsivity. Because the thermal expansion coefficient of the quartz-glass L-shaped lever and the steel sensor shell is different, the temperature effect is compensated for by optimizing the dimension parameters. Theoretical analysis is presented, and the experimental results show that an ultrahigh pressure responsivity of 244 pm/kPa and a low temperature responsivity of 2.8 pm/degrees C are achieved. (c) 2009 Society of Photo-Optical Instrumentation Engineers. [DOI 10.1117/1.3081058]

Polarized photoluminescence and temperature-dependent - Photoluminescence study of InAs quantum wires on InP(001)

InAs quantum wires (QWRs) have been fabricated on the InP(001), which has been evidenced by TEM and polarized photoluminescence measurements (PPL). The monlayer-splitting peaks (MSPs) in the PL spectrum of InAs QWRs can be clearly observed at low temperature measurements. Supposing a peak-shift of MSP identical to that of bulk material, we obtain the thermal activation energies of up to 5 MSPs. The smaller thermal activation energies for the MSPs of higher energy lead to the fast red-shift of PL peak as a whole.

A convenient way of determining the ferromagnetic transition temperature of metallic (Ga,Mn)As

We have studied magnetic and transport properties of insulating and metallic (Ga,Mn)As layers before and after annealing. A dramatic increase of the ferromagnetic transition temperature T-C by postgrowth annealing has been realized in both insulating and metallic (Ga,Mn)As. The as-grown insulating (Ga,Mn)As can be turned into metallic by the low-temperature annealing. For all the metallic (Ga,Mn)As, a characteristic feature in the temperature dependence of sheet resistance appears around T-C. This phenomenon may provide a simple and more convenient method to determine the T-C of metallic (Ga,Mn)As compared with superconducting quantum interference device (SQUID) measurement. Moreover, the T-C of the metallic (Ga,Mn)As obtained by this way is in good agreement with that measured by a SQUID magnetometer. (C) 2005 American Institute of Physics.

Demonstration of low-cost Si-based tunable long-wavelength resonant-cavity-enhanced photodetectors

A simple process for fabricating low-cost Si-based continuously tunable long-wavelength resonant-cavity-enhanced (RCE) photodetectors has been investigated. High-contrast SiO2/Si(Deltan similar to2) was employed as mirrors to eliminate the need to grow thick epitaxial distributed Bragg reflectors. Such high-reflectivity SiO2/Si mirrors were deposited on the as-grown InGaAs epitaxy layers, and then were bonded to silicon substrates at a low temperature of 350 C without any special treatment on bonding surfaces, employing silicate gel as the bonding medium. The cost is thus decreased. A thermally tunable Si-based InGaAs RCE photodetector operating at 1.3-1.6 mum was obtained, with a quantum efficiency of about 44% at the resonant wavelength of 1476 nm and a tuning range of 14.5 nm. It demonstrates a great potential for industry processes. (C) 2005 American Institute of Physics.

On the formation of well-aligned ZnO nanowall networks by catalyst-free thermal evaporation method

Two-dimensional ZnO nanowall networks were grown on ZnO-coated silicon by thermal evaporation at low temperature without catalysts or additives. All of the results from scanning electronic spectroscope, X-ray diffraction and Raman scattering confirmed that the ZnO nanowalls were vertically aligned and c-axis oriented. The room-temperature photoluminescence spectra showed a dominated UV peak at 378 nm, and a much suppressed orange emission centered at similar to 590 nm. This demonstrates fairly good crystal quality and optical properties of the product. A possible three-step, zinc vapor-controlled process was proposed to explain the growth of well-aligned ZnO nanowall networks. The pre-coated ZnO template layer plays a key role during the synthesis process, which guides the growth direction of the synthesized products. (C) 2007 Elsevier B.V. All rights reserved.