Aktivno lužnati kompoziti dobiveni od troske željezne i čelične industrije

Slag as a secondary raw material from metallurgy is most often heaped in slag disposal areas without any profit. This paper deals with alkali activated slag from iron and steel production which can be used in the building industry. Products of alkali slag activation fulfill the role of inorganic binders.Kao sekundarna sirovina, troska od metalurškog procesa najčešće se odlaže na deponije bez ikakve financijske dobiti. Ovaj rad se bavi lužnato aktiviranom troskom iz proizvodnje željeza i čelika, koja kao anorgansko vezivo može biti korištena u građevinskoj industriji

Photoinduced hole hopping through tryptophans in proteins

Hole hopping through tryptophan/tyrosine chains enables rapid unidirectional charge transport over long distances. We have elucidated structural and dynamical factors controlling hopping speed and efficiency in two modified azurin constructs that include a rhenium(I) sensitizer, Re(His)(CO)3(dmp)+, and one or two tryptophans (W1, W2). Experimental kinetics investigations showed that the two closely spaced (3 to 4 Å) intervening tryptophans dramatically accelerated long-range electron transfer (ET) from CuI to the photoexcited sensitizer. In our theoretical work, we found that time-dependent density-functional theory (TDDFT) quantum mechanics/molecular mechanics/molecular dynamics (QM/MM/MD) trajectories of low-lying triplet excited states of ReI(His)(CO)3(dmp)+–W1(–W2) exhibited crossings between sensitizer-localized (*Re) and charge-separated [ReI(His)(CO)3(dmp•–)/(W1•+ or W2•+)] (CS1 or CS2) states. Our analysis revealed that the distances, angles, and mutual orientations of ET-active cofactors fluctuate in a relatively narrow range in which the cofactors are strongly coupled, enabling adiabatic ET. Water-dominated electrostatic field fluctuations bring *Re and CS1 states to a crossing where *Re(CO)3(dmp)+←W1 ET occurs, and CS1 becomes the lowest triplet state. ET is promoted by solvation dynamics around *Re(CO)3(dmp)+(W1); and CS1 is stabilized by Re(dmp•–)/W1•+ electron/hole interaction and enhanced W1•+ solvation. The second hop, W1•+←W2, is facilitated by water fluctuations near the W1/W2 unit, taking place when the electrostatic potential at W2 drops well below that at W1•+. Insufficient solvation and reorganization around W2 make W1•+←W2 ET endergonic, shifting the equilibrium toward W1•+ and decreasing the charge-separation yield. We suggest that multiscale TDDFT/MM/MD is a suitable technique to model the simultaneous evolution of photogenerated excited-state manifolds

Tryptophan to Tryptophan Hole Hopping in an Azurin Construct.

Electron transfer (ET) between neutral and cationic tryptophan residues in the azurin construct [ReI(H126)(CO)3(dmp)](W124)(W122)CuI (dmp = 4,7-Me2-1,10-phenanthroline) was investigated by Born-Oppenheimer quantum-mechanics/molecular mechanics/molecular dynamics (QM/MM/MD) simulations. We focused on W124•+ ← W122 ET, which is the middle step of the photochemical hole-hopping process *ReII(CO)3(dmp•-) ← W124 ← W122 ← CuI, where sequential hopping amounts to nearly 10,000-fold acceleration over single-step tunneling (ACS Cent. Sci. 2019, 5, 192-200). In accordance with experiments, UKS-DFT QM/MM/MD simulations identified forward and reverse steps of W124•+ ↔ W122 ET equilibrium, as well as back ET ReI(CO)3(dmp•-) → W124•+ that restores *ReII(CO)3(dmp•-). Strong electronic coupling between the two indoles (≥40 meV in the crossing region) makes the productive W124•+ ← W122 ET adiabatic. Energies of the two redox states are driven to degeneracy by fluctuations of the electrostatic potential at the two indoles, mainly caused by water solvation, with contributions from the protein dynamics in the W122 vicinity. ET probability depends on the orientation of Re(CO)3(dmp) relative to W124 and its rotation diminishes the hopping yield. Comparison with hole hopping in natural systems reveals structural and dynamics factors that are important for designing efficient hole-hopping processes

Utilization of casting ladle lining enthalpy for heating gas savings in the course of ladle preheating

During the long-term staying of steel in ladle within the period from the tap until the end of continuous casting takes place a great amount of heat accumulates in lining. For its utilization is necessary to optimize heat operation of ladle lining. The demanded enthalpy of ladle before tap and the real enthalpy of ladle as things stand are needed for heating gas savings during the preheating. The enthalpy changes of ladle lining are in the course of their cycling in steelworks solved by the model of lining thermal state. For that purpose were conducted the operation measurements to find out the ladle lining thermal field within the whole technological flow

Light-Induced Nanosecond Relaxation Dynamics of Rhenium-Labeled Pseudomonas aeruginosa Azurins.

Time-resolved phosphorescence spectra of Re(CO)3(dmp)+ and Re(CO)3(phen)+ chromophores (dmp = 4,7-dimethyl-1,10-phenanthroline, phen = 1,10-phenanthroline) bound to surface histidines (H83, H124, and H126) of Pseudomonas aeruginosa azurin mutants exhibit dynamic band maxima shifts to lower wavenumbers following 3-exponential kinetics with 1-5 and 20-100 ns major phases and a 1.1-2.5 μs minor (5-16%) phase. Observation of slow relaxation components was made possible by using an organometallic Re chromophore as a probe whose long phosphorescence lifetime extends the observation window up to ∼3 μs. Integrated emission-band areas also decay with 2- or 3-exponential kinetics; the faster decay phase(s) is relaxation-related, whereas the slowest one [360-680 ns (dmp); 90-140 ns (phen)] arises mainly from population decay. As a result of shifting bands, the emission intensity decay kinetics depend on the detection wavelength. Detailed kinetics analyses and comparisons with band-shift dynamics are needed to disentangle relaxation and population decay kinetics if they occur on comparable timescales. The dynamic phosphorescence Stokes shift in Re-azurins is caused by relaxation motions of the solvent, the protein, and solvated amino acid side chains at the Re binding site in response to chromophore electronic excitation. Comparing relaxation and decay kinetics of Re(dmp)124K122Cu II and Re(dmp)124W122Cu II suggests that electron transfer (ET) and relaxation motions in the W122 mutant are coupled. It follows that nanosecond and faster photo-induced ET steps in azurins (and likely other redox proteins) occur from unrelaxed systems; importantly, these reactions can be driven (or hindered) by structural and solvational dynamics

Electron hopping through proteins

Biological redox machines require efficient transfer of electrons and holes for function. Reactions involving multiple tunneling steps, termed “hopping,” often promote charge separation within and between proteins that is essential for energy storage and conversion. Here we show how semiclassical electron transfer theory can be extended to include hopping reactions: graphical representations (called hopping maps) of the dependence of calculated two-step reaction rate constants on driving force are employed to account for flow in a rhenium-labeled azurin mutant as well as in two structurally characterized redox enzymes, DNA photolyase and MauG. Analysis of the 35 Å radical propagation in ribonucleotide reductases using hopping maps shows that all tyrosines and tryptophans on the radical pathway likely are involved in function. We suggest that hopping maps can facilitate the design and construction of artificial photosynthetic systems for the production of fuels and other chemicals

Hydraulic properties of ladle slags

The article presents results of examining of hydraulic properties of ladle slags formed during production of steel. The studied ladle slags were subjected to different cooling mode from the molten state. Based on the ability of the slag react with the water was assessed their hydraulic activity. The hydraulic properties are caused by the presence of minerals dicalcium silicate, tricalcium aluminate, mayenite, brownmillerite and dicalcium ferite. The emergence of required hydrating phases in the ladle slags is conditioned by a sufficient CaO content and their cooling rate. The contact the slag with water during processing and their ageing has a negative effect. The experiment has shown that the phase transformation of the mineral dicalcium silicate which occurs during cooling of the ladle slags cause their volume instability

Hydraulic properties of ladle slags

The article presents results of examining of hydraulic properties of ladle slags formed during production of steel. The studied ladle slags were subjected to different cooling mode from the molten state. Based on the ability of the slag react with the water was assessed their hydraulic activity. The hydraulic properties are caused by the presence of minerals dicalcium silicate, tricalcium aluminate, mayenite, brownmillerite and dicalcium ferite. The emergence of required hydrating phases in the ladle slags is conditioned by a sufficient CaO content and their cooling rate. The contact the slag with water during processing and their ageing has a negative effect. The experiment has shown that the phase transformation of the mineral dicalcium silicate which occurs during cooling of the ladle slags cause their volume instability