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PubMed2001

Enhancement of the sulfur capture capacity of limestones by the addition of Na2CO3 and NaCl.

The ability of Na2CO3 and NaCl to enhance the sulfur capture capacity of three limestones was evaluated via fixed-bed calcination and sulfation experiments. The tested limestones represent three different sulfation morphologies: unreacted-core, network, and uniformly sulfated. Treatment with aqueous or powdered Na2CO3 significantly increased the Ca-utilization for two stones which normally sulfate in an unreacted-core pattern (20% to 45%) and network pattern (33% to 49%). The increase was lower for the uniformly sulfated stone (44% to 48%). Na2CO3 treatment increased the number of macropores leading to uniform sulfation of all particles, nearly eliminating the normal strong dependence of utilization on limestone type and particle size. The effect of Na2CO3 is believed to be associated with formation of a eutectic melt which enhances ionic diffusion and accelerates molecular rearrangement of the CaO. Treatment with aqueous NaCl solution caused a decrease in utilization, probably due to formation of large grains and plugging of pores caused by formation of a large amount of eutectic melt. The effect of Na2CO3 is less sensitive than that of NaCl to the amount added and the combustion environment (temperature and gas composition). In addition, Na2CO3 neither promotes corrosion nor forms chlorinated byproducts, which are main concerns associated with NaCl. Thus, Na2CO3 appears to have significant advantages over NaCl for enhancement of limestone sulfur capture capacity in fluidized-bed combustors.

Adsorption↗

PubMed2006

Particle-wire-tube mechanism for carbon nanotube evolution.

The synthesis of carbon nanotubes (CNTs) has been proved to be greatly promoted by vapor metal catalysts, but the fast reaction feature and the required high-temperature environment involved in CNT evolution usually make it difficult for an insight into the evolution mechanism. Here, we successfully freeze the synthetic reaction at intermediary stages and observe the detailed morphologies and structures of the obtained intermediates and various objects related to carbon nanotubes. It is unveiled that there is a kindred evolution linkage among carbon nanoparticles, nanowires, and nanotubes in the vapor catalyst-involved synthetic processes: tiny carbon nanoparticles first form from a condensation of gaseous carbon species and then self-assemble into nanowires driven by an anisotropic interaction, and the nanowires finally develop into nanotubes, as a consequence of particle coalescence and structural crystallization. The function of metals is to promote the anisotropic interactions between the nanoparticles and the structural crystallization. An annealing transformation of carbon nanoparticles into nanotubes is also achieved, which gives further evidence for the evolution mechanism.

Journal Article↗

PubMed2005

Theoretical study on structures and stability of Si2CP isomers.

The structures, energetics, spectroscopies, and isomerization of various doublet Si2CP species are explored theoretically. In contrast to the previously studied SiC2N and SiC2P radicals that have linear SiCCN and SiCCP ground states, the title Si2CP radical has a four-membered-ring form cSiSiPC 1 (0.0 kcal/mol) with Si-C cross-bonding as the ground-state isomer at the CCSD(T)/6-311G(2df)//B3LYP/6-311G(d)+ZPVE level, similar to the Si2CN radical. The second low-lying isomer 2 at 11.6 kcal/mol has a SiCSiP four-membered ring with C-P cross-bonding, yet it is kinetically quite unstable toward conversion to 1 with a barrier of 3.5 kcal/mol. In addition, three cyclic species with divalent carbene character, i.e., cSiSiCP 7, 7' with C-P cross-bonding and cSiCSiP 8 with Si-Si cross-bonding, are found to possess considerable kinetic stability, although they are energetically high lying at 44.4, 46.5, and 41.4 kcal/mol, respectively. Moreover, a linear isomer SiCSiP 5 at 44.3 kcal/mol also has considerable kinetic stability and predominantly features the interesting cumulenic /Si=C=Si=P/* form with a slight contribution from the silicon-phosphorus triply bonded form /Si=C*-Si[triple bond]P/. The silicon-carbon triply bonded form *Si[triple bond]C-Si[triple bond]P/ has negligible contribution. All five isomers are expected to be observable in low-temperature environments. Their bonding nature and possible formation strategies are discussed. For relevant species, the QCISD/6-311G(d) and CCSD(T)/6-311+G(2df) (single-point) calculations are performed to provide more reliable results. The calculated results are compared to those of the analogous C3N, C3P, SiC2N, and Si2CN radicals with 17 valence electrons. Implications in interstellar space and P-doped SiC vaporization processes are also discussed.

Journal Article↗

PubMed2005

Low temperature NH(X 3sigma-) radical reactions with NO, saturated, and unsaturated hydrocarbons studied in a pulsed supersonic laval nozzle flow reactor between 53 and 188 K.

The reactions of ground-state imidogen radicals (NH(X 3sigma-)) with NO and select saturated and unsaturated hydrocarbons have been measured in a pulsed supersonic expansion Laval nozzle flow reactor in the temperature range 53-188 K. The rate coefficients for the NH + NO system display negative temperature dependence in the temperature regime currently investigated and a global temperature-dependent fit is best represented in a modified power law functional form, with k1(NH + NO) = (4.11 +/- 0.31) x 10(-11) x (T/300)(-0.30+/-0.17) x exp(77+/-21/T) cm3/s. The reactions of NH with ethylene, acetylene, propene, and diacetylene were measured over the temperature range 53-135 K. In addition, the reactions of NH with methane and ethane were also measured at 53 K, for reasons discussed later. The temperature dependence of the reactions of NH with the unsaturated hydrocarbons are fit using power law expressions, k(T) = A(T/300)(-n), and are as follows: k4 = (2.3 +/- 1.2) x 10(-12) x (T/300)(-1.09+/-0.33) cm3/s, k5 = (4.5 +/- 0.3) x 10(-12) x (T/300)(-1.07+/-0.04) cm3/s, k6 = (5.6 +/- 1.9) x 10(-12) x (T/300)(-1.23+/-0.21) cm3/s, and k7 = (7.4 +/- 1.8) x 10(-12) x (T/300)(-1.23+/-0.15) cm3/s for ethylene, acetylene, propene, and diacetylene, respectively. The rate for NH + ethane at 53 K is measured to be k3 = (6.8 +/- 1.7) x 10(-12) cm3/s, while that for methane at the same temperature represents an upper bound of k2 < or = (1.1 +/- 4.3) x 10(-12) cm3/s, as this is at the limits of measurement with our current technique. The behavior of these systems throughout the temperature range explored indicates that these reactions occur over a potential energy surface without an appreciable barrier through a complex formation mechanism. Implications for chemistry in low temperature environments where these species are found are briefly discussed.

Journal Article↗

PubMed2005

A large dust/ice ratio in the nucleus of comet 9P/Tempel 1.

Comets spend most of their life in a low-temperature environment far from the Sun. They are therefore relatively unprocessed and maintain information about the formation conditions of the planetary system, but the structure and composition of their nuclei are poorly understood. Although in situ and remote measurements have derived the global properties of some cometary nuclei, little is known about their interiors. The Deep Impact mission shot a projectile into comet 9P/Tempel 1 in order to investigate its interior. Here we report the water vapour content (1.5 10(32) water molecules or 4.5 10(6) kg) and the cross-section of the dust (330 km2 assuming an albedo of 0.1) created by the impact. The corresponding dust/ice mass ratio is probably larger than one, suggesting that comets are 'icy dirtballs' rather than 'dirty snowballs' as commonly believed. High dust velocities (between 110 m s(-1) and 300 m s(-1)) imply acceleration in the comet's coma, probably by water molecules sublimated by solar radiation. We did not find evidence of enhanced activity of 9P/Tempel 1 in the days after the impact, suggesting that in general impacts of meteoroids are not the cause of cometary outbursts.

Journal Article↗

PubMed2006

Hot crenarchaeal viruses reveal deep evolutionary connections.

The discovery of archaeal viruses provides insights into the fundamental biochemistry and evolution of the Archaea. Recent studies have identified a wide diversity of archaeal viruses within the hot springs of Yellowstone National Park and other high-temperature environments worldwide. These viruses are often morphologically unique and code for genes with little similarity to other known genes in the biosphere, a characteristic that has complicated efforts to trace their evolutionary history. Comparative genomics combined with structural analysis indicate that spindle-shaped virus lineages might be unique to the Archaea, whereas other icosahedral viruses might share a common lineage with viruses of Bacteria and Eukarya. These studies provide insights into the evolutionary history of viruses in all three domains of life.

Archaeal Viruses↗

PubMed2003

Structure and function of the globin and globin gene from the Antarctic mollusc Yoldia eightsi.

The mechanism of adaptation of haemoglobin from the Antarctic mollusc Yoldia eightsi to its low-temperature environment is a decrease in the oxygen affinity via an increased ligand-dissociation rate. At 2 degrees C this haemoglobin has an oxygen affinity similar to other haemoglobins at 25 degrees C. At 25 degrees C, Yoldia haemoglobin shows a low oxygen affinity, resembling that of human deoxyhaemoglobin. The mechanism involves a lower binding energy to oxygen, suggesting a loss or weakening of the usual hydrogen bond, leading to a higher oxygen-dissociation rate. However, Yoldia haemoglobin has the usual distal and proximal histidines, so the primary structure alone does not provide an obvious explanation for the low affinity. The CO-binding kinetics are biphasic, with the fraction of slow phase increasing at higher protein concentrations, indicating the formation of dimers or a higher level of polymerization. The protein-protein interaction appears to be of hydrophobic nature, since it can be partially reversed by addition of ethylene glycol as co-solvent. While the CO-association rates differ by a factor of 10, the oxygen equilibrium data could be simulated with a single affinity. The Yoldia haemoglobin gene contains three introns, interrupting the coding region at position NA1.2, B12.2 and G7.0. The conservation of the B12.2 and G7.0 introns is in contrast with the unprecedented NA1.2 intron. Phylogenetic analyses reveal a gene tree where the Yoldia haemoglobin gene is separated from other mollusc globin genes, confirming the specific adaptation of the Yoldia haemoglobin.

Amino Acid Sequence↗

PubMedDate not supplied

Induced differentiation of ovine foetal gonocytes after grafting in the scrotum of nude mice.

This work was designed to elucidate, in foetal ovine testis, whether the reason why gonocytes do not differentiate into spermatogonia and do not initiate spermatogenesis is due to inadequate foetal environment (temperature and/or hormonal balance) or if somatic testicular cell proliferation is a prerequisite for initiation of male meiosis. The development and differentiation of gonocytes were analysed by grafting 60-day-old foetal ovine tests into the scrotum of immunotolerant adult Nude mice. Forty days after grafting, nine of the ten grafted testes had survived but had not increased in weight as compared to 60-day-old tests. Moreover, only one third of the graft was occupied by testicular tissue, in which the relative proportions of intertubular tissue and sex cords were not altered when compared with those of normal foetal testes. The remainder of the graft was occupied by teratoma. The total number of Leydig (-80%) cells, Sertoli (-66%) cells, gonocytes (-90%) and the total length of sex cords (-63%) per grafted testis were always significantly reduced (P < 0.02), whereas the sex cords were significantly increased in diameter (+36%; P = 0.02) as compared to those of non-grafted 60-day-old foetuses. However, in seven out of the nine testes, type A spermatogonia were obtained and in two of the seven a few type B or leptotene primary spermatocytes could be observed. The grafting of foetal testis in an adult scrotum induces differentiation of gonocytes into spermatogonia, independently of proliferation of Sertoli and Leydig cells.

Animals↗

PubMed1971

The elastomeric rack in biology.

A model designated "The elastomeric rack" is discussed with reference to the mechanism of enzyme catalysis and the necessity of large protein molecules in the process. This model, which represents an extension of the earlier "Rack mechanism," stems from experimental evidence demonstrating large volume changes of activation or of reaction accompanying various biochemical reactions and more complicated physiological processes. For reasons discussed, the volume changes, as revealed through the influence of increased hydrostatic pressure on reaction rates and equilibria, prove that there are large conformational changes in the protein which, because of numerous cross links in a complex network, lead to additive stress on the substrate-enzyme complex, and thereby to increased reactivity. The manner in which the model serves to account for the influence of changes in the environment (temperature, pressure, chemical composition, electrical fields) on the activity of the protein catalyst, and the modifying action of particular inhibitory or activating substances, alone or in combination, is briefly discussed. The bearing of various considerations on protein denaturation, excitation of nerve, contraction of muscle, specific precipitation, and the divers physiological processes in living cells, including mutation, cancer, and the degenerative diseases of aging, is also briefly discussed.

Catalysis↗

PubMed1995

Effect of the arrangement of tandem repeating units of class A amphipathic alpha-helixes on lipid interaction.

Exchangeable apolipoproteins possess tandem repeating units of class A amphipathic helical segments and many of them are linked together by proline residues. To understand the optimal arrangement of the amphipathic helixes for lipid association, we have studied the interactions of three model class A amphipathic helical peptides with lipids. The three peptides are: 37pA, a dimer of 18A (DWLKAFYDKVAEKLKEAF) linked together by a Pro (18A-Pro-18A); 37aA, a dimer of 18A linked together by an Ala (18A-Ala-18A); and 36A, a dimer of 18A without any linker residue (18A-18A). Circular dichroism (CD) spectra showed that the peptides are predominantly alpha-helical in aqueous and lipid environments. Temperature dependent CD studies indicated that in buffer helix stability decreases in the order 36A > 37aA > 37pA; however, in the presence of dimyristoyl phosphatidylcholine (DMPC), the above order is reversed. The retention times of the peptides on a C18 reversed-phase high performance liquid chromatography column decreased in the order 36A > 37aA > 37pA, consistent with the lengths of the nonpolar faces of the alpha-helixes being in the same order; the retention time of the parent 18A was shorter than 37pA. While 37pA adsorbed to egg phosphatidylcholine monolayers most strongly, the degree and rate of association of 36A were significantly lower. Differential scanning calorimetry indicated that, while 37pA was most effective in reducing the enthalpy of the gel to liquid-crystalline phase transition of DMPC multilamellar vesicles, 36A was least effective; 36A was even less effective than 18A. Fluorescence quenching experiments with iodide and acrylamide indicated that, in the presence of DMPC, Trp residues in 36A are most exposed to the quenchers while in 37pA they are least exposed. In the presence of DMPC, shielding of Trp in 18A from the quenchers was more than that observed with Trp residues in 36A. The results of this study suggest that the arrangement of tandem repeating amphipathic helical units which results in the formation of a class A amphipathic helix with a nonpolar face longer than five or six turns reduces the ability of the helix to associate with phospholipid.

Amino Acid Sequence↗

PubMed2000

tRNA recognition of tRNA-guanine transglycosylase from a hyperthermophilic archaeon, Pyrococcus horikoshii.

In the biosynthesis of archaeosine, archaeal tRNA-guanine transglycosylase (TGT) catalyzes the replacement of guanine at position 15 in the D loop of most tRNAs by a free precursor base. We examined the tRNA recognition of TGT from a hyperthermophilic archaeon, Pyrococcus horikoshii. Mutational studies using variant tRNA(Val) transcripts revealed that both guanine and its location (position 15) were strictly recognized by TGT without any other sequence-specific requirements. It appeared that neither the global L-shaped structure of a tRNA nor the local conformation of the D loop contributed to recognition by TGT. A minihelix composed of the acceptor stem and D arm of tRNA(Val), designed as a potential minimal substrate, failed to serve as a substrate for TGT. Only a minihelix with mismatched nucleotides at the junction between the two domains served as a good substrate, suggesting that mismatched nucleotides in the helix provide the specific information that allows TGT to recognize the guanine in the D loop. Our findings indicate that the tRNA recognition requirements of P. horikoshii TGT are sufficiently limited and specific to allow the enzyme to recognize efficiently any tRNA species whose structure is not fully stabilized in an extremely high temperature environment.

Anticodon↗

PubMed2003

Fire fighting and its influence on the body.

Working conditions for fire fighters can be described according to the environment temperature and the incident radiant heat flux. Measurements for this study in buildings for fire fighting training have shown that fire fighters are typically exposed to radiant heat fluxes of between 5 and 10 kWm(-2) during this kind of exercise. The heat load can nevertheless be much higher. In one case, 42 kWm(-2) was measured. The temperatures reached between 100 and 190 degrees C at 1 m above ground, going up to 278 degrees C in one case. Human trials have been performed with 17 fire fighters. After exercises (about 15 min) in a heated room, the mean core temperature of the fire fighters rose by 0.6 degrees C with a surrounding temperature of 31 degrees C and 1.0 degrees C with 38 degrees C. The sweat production varied from 0.7 to 2.1 lh(-1); 16% to 45% of sweat remained in the clothing layers. During the exercises in the training buildings, a mean of 48 degrees C has been measured between fire fighters' clothing and workwear. These conditions lead to an increase of the relative humidity in all the jackets up to 100%. When the fire fighters came out of the fire, the humidity remained at this level in the PVC coated jackets while it was in some cases strongly reduced in breathable jackets.

Fires↗

PubMed2006

Day-night differences in membrane-bound pyroglutamyl-2-naphthylamide-hydrolyzing activity in rat hypothalamus, pituitary, and retina.

Membrane-bound pyroglutamyl-2-naphthylamide-hydrolyzing enzyme activity was analyzed fluorometrically in the anterior hypothalamus, pituitary, and retina of adult male rats to investigate day-night differences. Six groups (n=6 per group) were assessed--three during the light span and three during the dark span--under a standard 12 h-12 h light-dark cycle (light on from 07:00 to 19:00 h) and controlled temperature environment, with food and water available ad libitum. In the hypothalamus, enzyme activity levels were higher for time points of the dark than the light period. In contrast, the pituitary and retina exhibited the highest levels at the time points of the light period. The pituitary and retina also exhibited significant differences between the clock-hour means of the light period. Day-night differences in membrane-bound pyroglutamyl-2-naphthylamide-hydrolyzing activity may reflect differences in its susceptible endogenous substrates.

Aminopeptidases↗

PubMed1994

Myofibrillar protein from different muscle fiber types: implications of biochemical and functional properties in meat processing.

Texture, moisture retention, and tenderness of processed muscle foods are influenced by the functionality of myofibrillar protein. Recent studies have revealed large variations in processing quality between red and white muscle groups that can be attributed to differences in the functional properties of myofibrillar protein associated with the type of fiber. Myofibrillar proteins from fast- and slow-twitch fibers exhibit different biochemical and rheological characteristics and form gels with distinctly different viscoelastic properties and microstructures. The existence and wide distribution of the numerous myosin isoforms in different muscle and fiber types contribute to the various functional behaviors of myofibrillar protein. The different sensitivities of fast and slow myofibrillar proteins to pH, ionic environment, temperature, and other external factors have been well documented and illustrate the importance of adjusting meat processing conditions, according to fiber type profile to achieve maximum protein functionalities, and hence, uniform quality of the final muscle foods.

Actins↗

PubMed1994

Chrysotile: its occurrence and properties as variables controlling biological effects.

Chrysotile formation arises through serpentinization of ultramafics and silicified dolomitic limestones. Rock types tend to control the trace metal content and both the nature and amounts of admixed minerals in the ore, such as fibrous brucite (nemalite) and tremolite. Some associated minerals and trace metals are thought to play a role in biological potential. Tremolite, one of the important associated minerals, may occur with different morphological forms, called habits. These habits range from asbestiform (tremolite asbestos) to common blocky or non-fibrous form (tremolite cleavage fragments). The latter is most common in nature. Tremolite in chrysotile ore varies in habit and concentration, both factors determining the degree of risk following inhalation. Tremolite fibre is thought to be important in relation to the occurrence of mesothelioma. Chrysotile fibrils may vary in diameter. Dust clouds generated following manipulation vary in fibre number and surface area. Chrysotile fibres exhibit a range of physical characteristics. The fibre may be non-flexible ('stiff') and low in tensile strength ('brittle'), and may lack an ability to curl. This fibre, referred to as 'harsh', sheds water more quickly than its curly, flexible 'soft' variety. The behaviour of the harsh fibres is more amphibole-like and their splintery nature suggests an enhanced inhalation potential. Slip fibre ore from Canada tends to contain more fibrous brucite (nemalite) than cross-fibre ore in the same mine. Industrial manipulation, which includes chemical treatment, heating and milling, may impart new surface properties to chrysotile dusts. Biological potential may be enhanced (opening of fibre bundles) or reduced (disruption of surface bonds and lessened ability to interact with organic moieties). Leaching of magnesium from chrysotile occurs at a pH less than about 10. Chrysotile has been demonstrated to lose magnesium in vivo and undergo clearance from the lung. The biological potential of magnesium-depleted chrysotile is much reduced, or even eliminated. Reduction of mesothelioma-inducing and cytotoxic potential has been observed and quantified experimentally. Use of chrysotile products in high-temperature environments may heat the mineral to the point where it undergoes alteration of properties, especially by dehydroxylation. Chrysotile ore may vary in properties and associated minerals: it may form aerosols with different size distributions, especially fibre/fibril diameters and surface areas; it may be associated with varying quantities of tremolite (with differing habits); it may be manipulated both industrially and environmentally to yield surfaces with different properties and, hence, differing biological potentials. Chrysotile's properties may vary from place to place and among different user industries.

Asbestos, Amphibole↗

PubMed2025

Mining thermophile photosynthesis genes: a synthetic operon expressing Chloroflexota species reaction center genes in Rhodobacter sphaeroides.

Photosynthesis is the foundation of the vast majority of life systems, and therefore the most important bioenergetic process on earth, and the greatest diversity in photosynthetic systems are found in microorganisms. However, understanding of the biophysical and biochemical processes that transduce light to chemical energy has derived from the relatively small subset of proteins from microbes that are amenable to cultivation, in contrast to the huge number of microbial DNA sequences encoding proteins that catalyze the initial photochemical reactions that has been deposited in databases, such as from metagenomics. We describe the use of a Rhodobacter sphaeroides laboratory strain for expression of heterologous photosynthesis genes to demonstrate the feasibility of mining this resource, focusing on hot spring Chloroflexota gene sequences. Using a synthetic operon of genes, we produced a photochemically active complex of reaction center proteins in our biological system. We also present bioinformatic analyses of anoxygenic type II reaction center sequences from metagenomic samples collected from hot (42-90° C) springs available through the JGI IMG database, to generate a resource of diverse sequences that potentially are adapted to photosynthesis at such temperatures. These data provide a view into the natural diversity of anoxygenic photosynthesis, through a lens focused on high-temperature environments. The approach we took to express such genes can be applied for potential biotechnology purposes as well as for studies of fundamental catalytic properties of these heretofore inaccessible protein complexes.

Chloroflexota↗

PubMed2005

Complete genome sequence of the hyperthermophilic archaeon Thermococcus kodakaraensis KOD1 and comparison with Pyrococcus genomes.

The genus Thermococcus, comprised of sulfur-reducing hyperthermophilic archaea, belongs to the order Thermococcales in Euryarchaeota along with the closely related genus Pyrococcus. The members of Thermococcus are ubiquitously present in natural high-temperature environments, and are therefore considered to play a major role in the ecology and metabolic activity of microbial consortia within hot-water ecosystems. To obtain insight into this important genus, we have determined and annotated the complete 2,088,737-base genome of Thermococcus kodakaraensis strain KOD1, followed by a comparison with the three complete genomes of Pyrococcus spp. A total of 2306 coding DNA sequences (CDSs) have been identified, among which half (1165 CDSs) are annotatable, whereas the functions of 41% (936 CDSs) cannot be predicted from the primary structures. The genome contains seven genes for probable transposases and four virus-related regions. Several proteins within these genetic elements show high similarities to those in Pyrococcus spp., implying the natural occurrence of horizontal gene transfer of such mobile elements among the order Thermococcales. Comparative genomics clarified that 1204 proteins, including those for information processing and basic metabolisms, are shared among T. kodakaraensis and the three Pyrococcus spp. On the other hand, among the set of 689 proteins unique to T. kodakaraensis, there are several intriguing proteins that might be responsible for the specific trait of the genus Thermococcus, such as proteins involved in additional pyruvate oxidation, nucleotide metabolisms, unique or additional metal ion transporters, improved stress response system, and a distinct restriction system.

Amino Acid Substitution↗

PubMed2000

Optical emissions in a sonoluminescing bubble

We study how the mechanism of spontaneous decay of atoms (or molecules) in a sonoluminescing bubble (SLB) can be affected by the high density and high temperature environment resulting from the rapid collapse of the gas bubble immediately prior to light emission. We present a detailed study of the density of states of photons in multiple-layered spheres, which mimic various stages of a SLB. In particular, we found that the spontaneous decay rate could be strongly enhanced in the presence of a thin plasma shell inside the bubble, which was predicted recently in numerical hydrodynamic simulations of a SLB.

Journal Article↗