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This paper reviews the historical and applied literature on energy transitions from an integrated system-level framework. We synthesize the literature using a simple energy-service system framework to highlight the main problems and possible pathways for a transition to a decarbonized energy system. Recent literature suggests that the combination of demand-pull and technology-push policy instruments will be necessary to tip markets in favor of low-carbon energy alternatives. These studies illustrate that complex feedback mechanisms between the different components of an energy system, such as lock-in and push-back, complicate prescriptive policy design. The transition to a decarbonized energy system is one of the most pressing problems facing modern society. Energy systems are complex systems with many layers of feedback between social, technical, and institutional systems. Given these complexities, policy design and analysis must evolve to incorporate these feedbacks more explicitly.

S-Nitrosylation has emerged as an important pathway for dynamic post-translational regulation of many classes of proteins. Now, the reversible insertion of NO into a copper–thiolate bond has been observed under physiologically relevant conditions using an engineered azurin. DFT calculation indicates that the reaction proceeds via a radical combination mechanism.

Devices that condense and disinfect water vapour to provide chilled drinking water in office environments, so-called 'air water generators' (AWGs), are being marketed as environmentally friendly alternatives to the traditional bottled water cooler. We sought to examine this claim. The approach adopted was a preliminary life cycle assessment with performance indicators for the use of energy and water and the emission of greenhouse gases. We compared an AWG with its main market competitor, the traditional bottled water cooler and a simple refrigerator containing a jug of water. Modelling was based on Australian conditions and energy supply. To manage possible scope uncertainty, we borrowed the idea of 'triangulation' as defined in the social sciences. We found that without a renewable energy supply, the claim of environmental superiority is not supported by quantitative analysis. For each indicator, the AWG's score was typically two to four times higher than the alternatives. Energy consumption was the key issue driving all three indicators. Considering the principal environmental issues related to these systems, air-to-water machines significantly underperform bottled water coolers. A simple refrigerator has the capacity to perform multiple functions and therefore outperform both the bottled and atmospheric water options once allocation of burdens is considered. These conclusions are supported by all three perspectives examined to manage uncertainty.

Tyramine β-monooxygenase (TBM) is a member of a family of copper monooxygenases containing two noncoupled copper centers, and includes peptidylglycine monooxygenase and dopamine β-monooxygenase. In its Cu(II) form, TBM is coordinated by two to three His residues and one to two non-His O/N ligands consistent with a [CuM(His)2(OH2)2–CuH(His)3(OH2)] formulation. Reduction to the Cu(I) state causes a change in the X-ray absorption spectroscopy (XAS) spectrum, consistent with a change to a [CuM(His)2S(Met)–CuH(His)3] environment. Lowering the pH to 4.0 results in a large increase in the intensity of the Cu(I)–S extended X-ray absorption fine structure (EXAFS) component, suggesting a tighter Cu–S bond or the coordination of an additional sulfur donor. The XAS spectra of three variants, where the CuM Met471 residue had been mutated to His, Cys, and Asp, were examined. Significant differences from the wild-type enzyme are evident in the spectra of the reduced mutants. Although the side chains of His, Cys, and Asp are expected to substitute for Met at the CuM site, the data showed identical spectra for all three reduced variants, with no evidence for coordination of residue 471. Rather, the K-edge data suggested a modest decrease in coordination number, whereas the EXAFS indicated an average of two His residues at each Cu(I) center. These data highlight the unique role of the Met residue at the CuM center, and pose interesting questions as to why replacement by the cuprophilic thiolate ligand leads to detectable activity whereas replacement by imidazole generates inactive TBM. Electronic supplementary material The online version of this article (doi:10.1007/s00775-010-0677-3) contains supplementary material, which is available to authorized users.

The periplasmic metallochaperone CusF coordinates Cu(I) and Ag(I) through a unique site consisting of a Met(2)His motif as well as a Cu(I)-pi interaction between a nearby tryptophan, W44, and the metal ion. Through mutational analyses we investigate here the role that W44 in CusF plays in metal coordination. Nuclear magnetic resonance spectra show that the specificity of CusF for Cu(I) and Ag(I) is not altered by mutation of W44. X-ray absorption spectroscopy studies reveal that W44 protects the bound Cu(I) from oxidation as well as from adventitious ligands. Competition assays demonstrate that W44 does not significantly contribute to the affinity of CusF for metal, but that substitution of W44 by methionine, which forms a fourth Cu(I) ligand, substantially increases the affinity. These studies indicate that W44 is important in maintaining a moderate-affinity and solvent-shielded three-coordinate environment for Cu(I), which has implications for the function of CusF as a metallochaperone.

The coordination environment of the Cu(B) center of the quinol oxidase from Acidianus ambivalens, a type B heme-copper oxygen reductase, was investigated by Fourier transform (FT) IR and extended X-ray absorption fine structure (EXAFS) spectroscopy. The comparative structural chemistry of dinuclear Fe-Cu sites of the different types of oxygen reductases is of great interest. Fully reduced A. ambivalens quinol oxidase binds CO at the heme a (3) center, with nu(CO)=1,973 cm(-1). On photolysis, the CO migrated to the Cu(B) center, forming a Cu (B) (I) -CO complex with nu(CO)=2,047 cm(-1). Raising the temperature of the samples to 25 degrees C did not result in a total loss of signal in the FTIR difference spectrum although the intensity of these signals was reduced sevenfold. This observation is consistent with a large energy barrier against the geminate rebinding of CO to the heme iron from Cu(B), a restricted limited access at the active-site pocket for a second binding, and a kinetically stable Cu(B)-CO complex in A. ambivalens aa (3). The Cu(B) center was probed in a number of different states using EXAFS spectroscopy. The oxidized state was best simulated by three histidines and a solvent O scatterer. On reduction, the site became three-coordinate, but in contrast to the bo (3) enzyme, there was no evidence for heterogeneity of binding of the coordinated histidines. The Cu(B) centers in both the oxidized and the reduced enzymes also appeared to contain substoichiometric amounts (0.2 mol equiv) of nonlabile chloride ion. EXAFS data of the reduced carbonylated enzyme showed no difference between dark and photolyzed forms. The spectra could be well fit by 2.5 imidazoles, 0.5 Cl(-) and 0.5 CO ligands. This arrangement of scatterers would be consistent with about half the sites remaining as unligated Cu(his)(3) and half being converted to Cu(his)(2)Cl(-)CO, a 50/50 ratio of Cu(his)(2)Cl(-) and Cu(his)(3)CO, or some combination of these formulations.

Although in a previous study we showed that caffeine and theobromine were the main psychopharmacologically active constituents in a 50-g bar of chocolate, mere activity does not guarantee a role in our liking for the food. Our aim was to see if liking for a drink repeatedly paired with these amounts of caffeine and theobromine would increase compared to a placebo-paired drink. Participants (n=64) consumed a ‘novel’ drink + treatment capsule on six non-consecutive mornings using a double-blind, placebo-controlled independent-sample design. Aspects of liking and intensity of various sensory descriptors for these drinks were measured at every drink collection. Treatment capsules contained either an ecologically relevant dose combination of 19-mg caffeine and 250-mg theobromine or a placebo. Liking for the drink paired with the methylxanthine-containing capsules increased over time compared to the placebo-paired drink. This highly significant effect was confirmed by subjective, retrospective changes in liking for the drink. Methylxanthines in amounts found in 50-g chocolate may well contribute to our liking for chocolate, especially to the more acquired taste for dark chocolate.

In the further development and understanding of heme-copper dioxygen reactivity relevant to cytochrome c oxidase O(2)-reduction chemistry, we describe a high-spin, five-coordinate dioxygen (peroxo) adduct of an iron(II)-copper(I) complex, [((6)L)Fe(II)Cu(I)](BArF(20)) (1), where (6)L is a tetraarylporphyrinate with a tethered tris(2-pyridylmethyl)amine chelate for copper. Reaction of 1 with O(2) in MeCN affords a remarkably stable [t(1/2) (rt; MeCN) approximately 60 min] adduct, [((6)L)Fe(III)-(O(2) (2-))-Cu(II)](+) (2) [EPR silent; lambda(max)=418 (Soret), 561 nm], formulated as a peroxo complex based on manometry (1:O(2)=1:1; spectrophotometric titration, -40 degrees C, MeCN), mass spectrometry {MALDI-TOF-MS: (16)O(2), m/z 1191 ([((6)L)Fe(III)-((16)O(2) (2-))-Cu(II)](+)); (18)O(2), m/z 1195}, and resonance Raman spectroscopy (nu((O-O))=788 cm(-1); Delta(16)O(2)/(18)O(2)=44 cm(-1); Delta(16)O(2)/(16/18)O(2)=22 cm(-1)). (1)H and (2)H NMR spectroscopy (-40 degrees C, MeCN) reveals that 2 is the first heme-copper peroxo complex which is high-spin, with downfield-shifted pyrrole resonances (delta(pyrrole)=75 ppm, s, br) and upfield shifted peaks at delta= -22, -35, and -40 ppm, similar to the pattern observed for the mu-oxo complex [((6)L)Fe(III)-O-Cu(II)](BAr(F)) (3) (known S=2 system, antiferromagnetically coupled high-spin Fe(III) and Cu(II)). The corresponding magnetic moment measurement (Evans method, CD(3)CN, -40 degrees C) also confirms the S=2 spin state, with mu(B)=4.9. Structural insights were obtained from X-ray absorption spectroscopy, showing Fe-O (1.83 A) and Cu-O (1.882 A) bonds, and an Fe...Cu distance of 3.35(2) A, suggestive of a mu-1,2-peroxo ligand present in 2. The reaction of 2 with cobaltocene gives 3, differing from the observed full reduction seen with other heme-Cu peroxo complexes. Finally, thermal decomposition of 2 yields 3, with concomitant release of 0.5 mol O(2) per mol 2, as confirmed quantitatively by an alkaline pyrogallol dioxygen scavenging solution.

Binding of the Cu(I)-specific ligands 2,6-dimethylphenyl isocyanide (DIMPI) and isopropyl isocyanide (IPI) to the reduced form of peptidylglycine monooxygenase (PHM) is reported. Both ligands bind to the methionine-containing CuM center, eliciting FTIR bands at 2,138 and 2,174 cm(-1), respectively, but appear unable to coordinate at the histidine-containing CuH center in the wild-type enzyme. This chemistry parallels that previously observed for CO binding to the reduced PHM catalytic core (PHMcc). However, in contrast to the CO chemistry, peptide substrate binding did not induce binding of the isocyanide at CuH. XAS confirmed the binding of DIMPI at CuM via the observation of a short Cu-C interaction at 1.87 A and by the lengthening of the Cu-S(methionine) bond length by 0.06 A. Similarly, FTIR studies on DIMPI binding to the M314I and H172A mutant forms of reduced PHMcc confirmed the assignment of the 2,138-cm(-1) IR band as a CuM-DIMPI complex, but surprisingly also showed DIMPI binding to CuH, as indicated by a band at 2,148 cm(-1). An inorganic complex, [Cu(1,2-Me2Im)2(DIMPI)](PF6), was synthesized and its crystal structure was determined as a model for the interaction of isocyanides with imidazole-containing Cu(I) complexes. Comparison of EXAFS data for the protein and model suggests that DIMPI probably binds to CuM in a tilted fashion, similar to that of ethyl isocyanide binding to myoglobin.

X-ray absorption spectroscopy has been used to probe the local coordination of the copper centers in the oxidized and reduced states of the peptidylglycine monooxygenase catalytic core (PHMcc) in both the resting and substrate-bound forms of the enzyme. The results indicate that reduction causes significant changes in coordination number and geometry of both Cu centers (CuH and CuM). The CuH center changes from 4- or 5-coordinate tetragonal to a 2-coordinate configuration, with one of the three histidine ligands becoming undetectable by EXAFS (suggesting that it has moved away from the CuH by at least 0.3 A). The CuM center changes from 4- or 5-coordinate tetragonal to a trigonal or tetrahedral configuration, with an estimated 0.3-0.5 A movement of the M314 S ligand. Reduction also leads to loss of coordinated water from both of the coppers. Substrate binding has little or no effect on the local environment of the Cu centers in either oxidation state. These findings bring into question whether direct electron transfer between CuH and CuM via a tunneling mechanism can be fast enough to support the observed catalytic rate, and suggest that some other mechanism for electron transfer, such as superoxide channeling, should be considered.

The structure of the CuA-containing, extracellular domain of Thermus thermophilus ba3-type cytochrome c oxidase has been determined to 1.6 A resolution using multiple X-ray wavelength anomalous dispersion (MAD). The Cu2S2 cluster forms a planar rhombus with a copper-copper distance of 2.51 +/- 0.03 A. X-ray absorption fine-structure (EXAFS) studies show that this distance is unchanged by crystallization. The CuA center is asymmetrical; one copper is tetrahedrally coordinated to two bridging cysteine thiolates, one histidine nitrogen and one methionine sulfur, while the other is trigonally coordinated by the two cysteine thiolates and a histidine nitrogen. Combined sequence-structure alignment of amino acid sequences reveals conserved interactions between cytochrome c oxidase subunits I and II.

Carbon-13 decoupled 1H spin-echo nuclear magnetic resonance (NMR) spectra, with and without 13C population inversion, of extracts of Taenia crassiceps cysticerci incubated in media containing [3-(13C)]-pyruvate showed 13C enrichment in alanine, lactate, acetate, succinate, and citrate. Labeling in the latter three metabolites provides substantial evidence that the malic enzyme reaction in this cestode also functions in the direction opposite to that in which it is normally portrayed. The direct passage of pyruvate from the cytosol to the mitochondrion is suggested by the greater percentage of 13C detected in acetate relative to succinate.

Mortality from sepsis increases with delay in administration of antibiotics. The Surviving Sepsis Guidelines suggest that antibiotics are administered within 1 hour of diagnosis of severe sepsis and septic shock. This retrospective study investigated the time to appropriate antibiotics in patients with sepsis and identifies reasons for delay where possible.

The deformation substructure of TiAl (Llo type ordered lattice) tested in compression, and the factors determining it were investigated. Two types of dislocations take part in the plas-tic deformation, namely a/2 [110] and a/2 [Oil]. The latter type will disorder the Llo super-lattice and therefore would be expected to move in pairs as superdislocations. Some obser-vations are essentially in agreement with the predictions, however the large proportion and morphology of a/2 [O1l] dislocations observed was unexpected. Twins of the [112] (111) type play an important role in the deformation of the alloy, and the early stages of their formation have been recorded. Finally, equi-Schmid factor lines have been constructed in an attempt to evaluate the importance of the sense of the applied stress on the deformation capability of the alloy.

Ti-8 Al-1 Mo-1 V was tested in solvents containing chloride, bromide or iodide ions. It was found that the region II plateau velocity could be correlated with the inverse of the viscosity for several solvents. It seems most likely that this reflects the influence of the viscosity on the diffusion coefficient of some species involved in a mass transfer process which limits the crack growth. Associated tests were performed in which the potential, pH and concentration of Cl- were varied, in some of the same solutions as used for the viscosity tests. It is concluded from these tests that the absence of cathodic protection against cracking in solutions of low pH arises from an ohmic effect which isolates the crack tip from external potential control.

To gain insight into the factors which control the creep-rupture properties of powder metallurgical nickel-base superalloys at intermediate temperatures (650 to 775°C), a comparative study was conducted on the alloys AF115, modified MAR-M432 (B6) and modified IN100 (MERL76). Creep-rupture properties in these alloys were characterized in terms of the stress and temperature dependence of the secondary creep rate, eS, andrupture time,t R . Within the limited stress ranges used, the stress dependence of both eS andt R at 704°C can be represented by power laws eS andC n andt R =Mσ -p ; whereC,M, n, andp are constants. The stress exponentsn andp are approximately equal for both AF115 and B6 with values of 16 and 7, respectively. In the case of MERL76,n andp are different, with values of 15 and 5, respectively. The apparent activation energies,Q, are 700, 370 and 520 KJ mol-1 for AF115, B6 and MERL76, respectively. For these alloys, long creep-rupture lives are associated with large values ofn andQ. The sig-nificant differences inn andQ values between AF115 and B6 were related to creep re-covery processes for which the lattice misfit between the gamma and the gamma prime was identified to be an important parameter. However, the unequaln andp values in MERL76 compared with those in AF115 and B6, were traced to differences in fracture mode. Failures in AF115 and B6 were initiated at carbide particles at grain boundaries. In contrast, fracture in MERL76 was initiated at grain boundary triple junctions. The rupture lives of AF115 and B6 can be modeled reasonably well by the growth of cavities during secondary creep and propagation of a surface-nucleated crack during the tertiary creep.

This paper describes the influence of mictrostructure on the mechanical properties of the alloy Ti−11.5Mo−6Zr−4.5Sn. The phase transformations are similar to those that occur in binary Ti−Mo alloys containing 10 to 12 pct Mo. Thus, the β phase can be retained by quenching from above 1400°F. The β phase deforms in a complex manner, including mechanical twinning, and is characterized by low strength, high ductility, and high toughness. The ω phase, which also forms on quenching, is stable at temperatures up to 800°F. Yield strengths of up to 220 ksi have been measured in (β+ω) structures, the strength level being dependent on the size and volume fraction of the ω phase. In contrast, fracture toughness reaches a minimum value of }20 ksi\(\sqrt {in} \) when the ω particle size ≥100A. (β+α) structures show good combinations of yield strength and fracture toughness. Unfortunately, the best combinations are susceptible to stress-corrosion cracking in aqueous solutions containing halide ions.

The martensitic transformation and the effect of cobalt additions on important martensitic toughening parameters are being studied as a means of toughening NiAl alloys. Cobalt additions to NiAl martensite are seen to lower the Ms temperature, reduce the transformation strain anisotropy, and reduce the transformation temperature hysteresis (an indicator of interfacial mobility). Optimization of these parameters should allow martensitic transformation toughening processes to aid in overcoming the ambient temperature brittleness of NiAl alloys.

WE have studied the enzyme adenyl cyclase to extend the evidence that β-adrenoreceptors consist of at least two types, β-1 and β-2 (refs. 1-4.) Cyclic 3′,5′-AMP has been shown to be the intracellular mediator of the action of various hormones, including the catecholamines, and it has been suggested that adenyl cyclase is an integral part of the β-adrenoreceptor5,6. Thus adenyl cyclase preparations from certain tissues should differ in their responsiveness to β-adrenoreceptor agonists and antagonists in a manner analogous to the intact tissues. We have therefore examined the differential effects of some sympathomimetic amines and their antagonists on the activity of adenyl cyclase preparations from rat heart and lung.