Physical characterization of the rack effect and hydrogen bond networks in blue copper proteins

A summary of previous research is presented that indicates that the purpose of a blue copper protein's fold and hydrogen bond network, aka, the rack effect, enforce a copper(II) geometry around the copper(I) ion in the metal site. In several blue copper proteins, the C-terminal histidine ligand becomes protonated and detaches from the copper in the reduced forms. Mutants of amicyanin from Paracoccus denitrificans were made to alter the hydrogen bond network and quantify the rack effect by pK_a shifts.

The pK_a's of mutant amicyanins have been measured by pH-dependent electrochemistry. P94F and P94A mutations loosen the Northern loop, allowing the reduced copper to adopt a relaxed conformation: the ability to relax drives the reduction potentials up. The measured potentials are 265 (wild type), 380 (P94A), and 415 (P94F) mV vs. NHE. The measured pK_a's are 7.0 (wild type), 6.3 (P94A), and 5.0 (P94F). The additional hydrogen bond to the thiolate in the mutants is indicated by a red-shift in the blue copper absorption and an increase in the parallel hyperfine splitting in the EPR spectrum. This hydrogen bond is invoked as the cause for the increased stability of the C-terminal imidazole.

Melting curves give a measure of the thermal stability of the protein. A thermodynamic intermediate with pH-dependent reversibility is revealed. Comparisons with the electrochemistry and apoamicyanin suggest that the intermediate involves the region of the protein near the metal site. This region is destabilized in the P94F mutant; coupled with the evidence that the imidazole is stabilized under the same conditions confirms an original concept of the rack effect: a high energy configuration is stabilized at a cost to the rest of the protein.

Toxic blue-green algae: The "problem" in perspective

The incidence of blue-green algal blooms and surface scum-formation are certainly not new phenomena. Many British and European authors have been faithfully describing the unmistakable symptoms of blue-green algal scums for over 800 years. There is no disputing that blue-green algal toxins are extremely harmful. Three quite separate categories of compound have been separated: neurotoxins; hepatotoxins and lipopolysaccharides. There is a popular association between blue-green algae and eutrophication. Certainly the main nuisance species - of Microcystis, Anabaena and Aphanizomenon are rare in oligotrophic lakes and reservoirs. Several approaches have been proposed for the control of blue-green algae. Distinction is made between methods for discharging algae already present (eg algicides; straw bales; viruses; parasitic fungi and herbivorous ciliates), and methods for averting an anticipated abundance in the future (phosphorous control, artificial circulation etc).

The influence of blue-green algae on development of the zooplankton. [Translation of: Byull.mosk.Obshch.Ispyt.Prir.(Biol.) 67, 128-131, 1962]

Many have observed the reduction of the quantity of zooplankton in the presence of water blooms. It is known that in seas zooplankton as it were avoids places of accumulation of blue-green algae. By observations on one of the tributaries of the Rybinsk reservoir - the River Shumorovka - the authors tried by simultaneous collections to trace the changes in numbers, not only of zoo- and phytoplankton but also of bacteria. The plankton was collected by quantitative nets with suitable numbers of gauze and bacteria were taken account of by the method of direct calculation on membrane filters. It can be seen that the development of blue-green algae appears as an important factor, determining not only the intensity but also the direction of the process of production of zooplankton.

Discovery of viruses lysing blue-green algae in the Dneprovsk reservoirs. [Translation of: Water blooms (ed. A. V. Topachevskii) pp.171-174. Kiev, Naukova Dumka, 1968]

Viruses, which are characterised by a relative simplicity of chemical composition, are involved with all the groups of the animal and plant world. The discovery of viruses of lower organisms has special interest. Along with the already known viruses lysing bacteria and actinomycetes, viruses have been discovered in recent years which lyse algae. During investigations of water from water-bloom patches and of mud taken from zones of massive accumulation of blue-green algae in the Dneprovsk reservoirs, the authors obtained viruses lysing algae. The revealing of viruses producing lysis of blue-green algae, which one could use in the control of water-blooms, has the greatest interest. With this aim, samples of water were collected from various zones of water-bloom patches in the Kremenchug, Dneprovsk and Kukhov reservoirs. For viruses lysing algae we propose the name 'algophages'. Along with the existence of viruses of algae of the phage type, one cannot deny the possibility of the existence of viruses of another type, multiplying in the cells of algae and causing their virus illnesses.

Determination of dissolved oxygen in water with leukoberbelin-blue I. A quick Winkler method. [Translation from: Z.analyt.Chem. 262 97-99, 1972.]

The reaction of Mn(II) with water-dissolved oxygen, to a higher manganese hydroxide in an alkaline medium, as with the longstanding classic Winkler method, is the first step in the method described here. The assumption for faultless results by the conventional and modified Winkler method is clean water, which contains no organic substances by Mn(III) or Mn(IV). In many cases, however, eg. in river and lake-water tests, it can be seen with the naked eye that after some time the originally brown-coloured precipitate of manganese hydroxide becomes more and more colourless. Oxygen content was analysed in the water samples and evaluated by raising the amount of the leuko-base and giving the corresponding dilution of the colouring matter solution formed still higher oxygen contents can be measured.

I. Phosphorescence and the true lifetime of triplet states in fluid solutions. II. Why is condensed oxygen blue?

I. PHOSPHORESCENCE AND THE TRUE LIFETIME OF TRIPLET STATES IN FLUID SOLUTIONS

Phosphorescence has been observed in a highly purified fluid solution of naphthalene in 3-methylpentane (3-MP). The phosphorescence lifetime of C₁₀H₈ in 3-MP at -45 °C was found to be 0.49 ± 0.07 sec, while that of C₁₀D₈ under identical conditions is 0.64 ± 0.07 sec. At this temperature 3-MP has the same viscosity (0.65 centipoise) as that of benzene at room temperature. It is believed that even these long lifetimes are dominated by impurity quenching mechanisms. Therefore it seems that the radiationless decay times of the lowest triplet states of simple aromatic hydrocarbons in liquid solutions are sensibly the same as those in the solid phase. A slight dependence of the phosphorescence lifetime on solvent viscosity was observed in the temperature region, -60° to -18°C. This has been attributed to the diffusion-controlled quenching of the triplet state by residual impurity, perhaps oxygen. Bimolecular depopulation of the triplet state was found to be of major importance over a large part of the triplet decay.

The lifetime of triplet C₁₀H₈ at room temperature was also measured in highly purified benzene by means of both phosphorescence and triplet-triplet absorption. The lifetime was estimated to be at least ten times shorter than that in 3-MP. This is believed to be due not only to residual impurities in the solvent but also to small amounts of impurities produced through unavoidable irradiation by the excitation source. In agreement with this idea, lifetime shortening caused by intense flashes of light is readily observed. This latter result suggests that experiments employing flash lamp techniques are not suitable for these kinds of studies.

The theory of radiationless transitions, based on Robinson's theory, is briefly outlined. A simple theoretical model which is derived from Fano's autoionization gives identical result.

Il. WHY IS CONDENSED OXYGEN BLUE?

The blue color of oxygen is mostly derived from double transitions. This paper presents a theoretical calculation of the intensity of the double transition (a ¹Δ_g) (a ¹Δ_g)←(X ³Σ_g^-) (X ³Σ_g^-), using a model based on a pair of oxygen molecules at a fixed separation of 3.81 Å. The intensity enhancement is assumed to be derived from the mixing (a ¹Δ_g) (a ¹Δ_g) _~~~ (X ³Σ_g^-) (X ³Σ_u^-) and (a ¹Δ_g) (¹Δ_u) _~~~ (X ³Σ_g^-) (X ³Σ_g^-). Matrix elements for these interactions are calculated using a π-electron approximation for the pair system. Good molecular wavefunctions are used for all but the perturbing (B ³Σ_u^-) state, which is approximated in terms of ground state orbitals. The largest contribution to the matrix elements arises from large intramolecular terms multiplied by intermolecular overlap integrals. The strength of interaction depends not only on the intermolecular separation of the two oxygen molecules, but also as expected on the relative orientation. Matrix elements are calculated for different orientations, and the angular dependence is fit to an analytical expression. The theory therefore not only predicts an intensity dependence on density but also one on phase at constant density. Agreement between theory and available experimental results is satisfactory considering the nature of the approximation, and indicates the essential validity of the overall approach to this interesting intensity enhancement problem.

Calcite covering of sediment as a possible way of curbing blue-green algae

Natural calcite precipitation in lakes is a well-known control mechanism of eutrophication. In hard-water lakes, calcite deposits on the flat bottoms of shallow lakes and near the shores of deeper lakes resulted from biogenic decalcification during the millenia after the last glacial period. The objective of a new restoration technology is to intensify the natural process of precipitation by utilizing the different qualities of calcareous mud layers. In a pilot experiment in Lake Rudower See, East Germany, phosphorus-poor deeper layers of the sediments were flushed out and spread over the phosphorus-rich uppermost sediments, to promote the co- precipitation of calcite with phosphorus from the water-column.

Blue frontiers: managing the environmental costs of aquaculture

The report begins with an overview of the current status of world aquaculture. It then goes on to describe an approach for estimating the current combined biophysical resource demands of aquaculture for producer countries and regions. Following a comparison of these results with those available for other animal food production sectors the report then examines the consequences of likely future trends in production on the environmental impacts of aquaculture. Finally, the policy implications of the report’s findings are discussed along with the research agenda that should be pursued to meet the challenge of sustainable food production.

Rare earth doped beta-diketone complexes as promising high-density optical recording materials for blue optoelectronics

Some kinds of rare earth beta-diketone complexes with blue-violet light absorption edge were synthesized using the ligands of thenoyltrifluoroacctone (HTTA), 2, 2'-dipyridyl (BIPY) and different metal ions (Gd3+, Sm3+ and La3+). Their contents, structures and optoelectronic parameters were monitored by elemental analysis, MS, IR and UV spectra. The solubility of rare earth beta-diketone complexes in 2, 2, 3, 3-tetrafluoro-1-propanol (TFP) and absorption properties of their films in the region 300-800 nm were measured. The influence on the difference of absorption maximum from rare earth beta-diketone complexes to beta-diketone ligand by different metal ions was studied. In addition, the thermal stability of rare earth beta-diketone complexes was also reported. (C) 2005 Elsevier B.V. All rights reserved.

Design and construction of a static tester for blue ray optical storage

Blue ray optical storage is one of the important trends in the area of information storage, and attracts a number of researchers. Static tester for blue ray optical storage plays an important role in storage media research. We designed and constructed a static tester, in which modularization makes it very convenient to expand function. Employment of modulation/demodulation technique weakens test error so as to increase test precision. Focus move mode and the nano-positioners facilitate the relocation of recording marks. Only one laser with wavelength 406.7 nm is used. In this paper, system design and characteristics are represented in detail, and some experimental results are also given to show that the static tester can perform successfully, acting as research platform for blue ray optical storage. (c) 2005 Elsevier GmbH. All rights reserved.

Analysis on a new type magneto-optical disk for blue lasers

The conventional TbFeCo magneto-optical (MO) medium has a relatively smaller Kerr rotation angle in the blue region than in the red. With the recording wavelength gradually moving to the short wavelength, if TbFeCo is still used as recording medium, the conventional MO disk structure must be optimized to get a larger carrier to noise ratio (CNR). Sabi et al. have found that adding a metal layer attached to the TbFeCo film as thermal control layer is a useful way to get a high CNR. In this paper, we proved this through calculation, and carried out optimization of the new type of disk. Calculation results showed that the new structure is useful in preventing an excessive temperature increase, and has a better thermal response. (c) 2005 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic and thermal properties of nickel (II)-azo complexes with blue-violet light wavelength

A novel azo dye containing isoxazole ring and beta-diketone derivative (TIAD) and its two nickel (II) complexes (Ni (II)-ETIAD and Ni (II)-HTIAD) were synthesized in order to obtain a blue-violet light absorption and better thermal stability as a promising organic storage material for next generation of high density digital versatile disc-recordable (HD-DVD-R) systems that uses a high numerical aperture of 0.85 at 405 nm wavelength. Their structures were confirmed on the basis of elemental analysis, MS, FT-IR, UV-Vis and magnetic data. Their solubility in 2,2,3,3-tetrafluoro-1-propanol (TFP) and absorption properties of thin film were measured. The difference of absorption maximum from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated. (C) 2004 Elsevier Ltd. All rights reserved.

SbOx thin films used for write-once blue laser recording

SbOx thin films are deposited by reactive dc-magnetron sputtering from all antimony metal target in Ar+O-2 with the relative O-2 content 7%. It is found that the as-deposited films call represent a two-component system comprising amorphous Sb and amorphous Sb2O3. The crystallization of Sb is responsible for the changes of optical properties of the films. The results of the static, test show that the SbOx thin films have good writing sensitivity for blue laser beams and the recording marks are very clear and circular. High reflectivity contrast of about 41% is obtained at a writing power 6 mW and writing pulse width 300 ns. In addition, the films show a good stability after reading 10000 times.

Write-once blue laser recording using silicon doped SbOx thin films prepared by reactive dc-magnetron sputtering

Si:SbOx films have been deposited by reactive dc-magnetron sputtering from a Sb target with Si chips attached in Ar + O-2 with the relative O-2 content 7%. The as-deposited films contained Sb metal, Sb2O3, SiO, Si2O3 and SiO2. The crystallization of Sb was responsible for the changes of optical properties of the films. The results of the blue laser recording test showed that the films had good writing sensitivity for blue laser beam (406.7 nm), and the recording marks were still clear even if the films were deposited in air 60 days, which demonstrated that doping silicon in SbOx films can improve the stability of SbOx films. High reflectivity contrast of about 36% was obtained at a writing power 6 mW and writing pulse width 300 ns. (c) 2007 Elsevier B.V. All rights reserved.