An iterated greedy metaheuristic for the blocking job shop scheduling problem

In this paper we consider a job shop scheduling problem with blocking (BJSS) constraints. Blocking constraints model the absence of buffers (zero buffer), whereas in the traditional job shop scheduling model buffers have infinite capacity. There are two known variants of this problem, namely the blocking job shop scheduling with swap allowed (BWS) and the one with no swap allowed (BNS). This scheduling problem is receiving an increasing interest in the recent literature, and we propose an Iterated Greedy (IG) algorithm to solve both variants of the problem. IG is a metaheuristic based on the repetition of a destruction phase, which removes part of the solution, and a construction phase, in which a new solution is obtained by applying an underlying greedy algorithm starting from the partial solution. A comparison with recent published results shows that the iterated greedy algorithm outperforms other state-of-the-art algorithms on benchmark instances. Moreover it is conceptually easy to implement and has a broad applicability to other constrained scheduling problems.     

Ferrocene‐Promoted Long‐Cycle Lithium–Sulfur Batteries

Confining lithium polysulfide intermediates is one of the most effective ways to alleviate the capacity fade of sulfur‐cathode materials in lithium–sulfur (Li–S) batteries. To develop long‐cycle Li–S batteries, there is an urgent need for material structures with effective polysulfide binding capability and well‐defined surface sites; thereby improving cycling stability and allowing study of molecular‐level interactions. This challenge was addressed by introducing an organometallic molecular compound, ferrocene, as a new polysulfide‐confining agent. With ferrocene molecules covalently anchored on graphene oxide, sulfur electrode materials with capacity decay as low as 0.014 % per cycle were realized, among the best of cycling stabilities reported to date. With combined spectroscopic studies and theoretical calculations, it was determined that effective polysulfide binding originates from favorable cation–π interactions between Li⁺ of lithium polysulfides and the negatively charged cyclopentadienyl ligands of ferrocene.     

How suitable are scalp hair and toenail as biomonitors?

This paper describes the assessment of exposure levels to metals and possible workers' contamination in three galvanizing factories applying the same processes. Concerning the elements determined in air filters, 92.3% of them were also determined in hair and toenail samples: Ag, Al, As, Au, Cl, Cr, Cu, Fe, Mn, Na, Sb and Zn. These result point out that hair and toenail reflect the influence of the polluted environment on workers' health and can be useful as bioindicators in epidemiological studies. Instrumental neutron activation analysis was applied to all matrices which confirms its status as one of the most versatile analytical techniques.     

Studies of the Interaction of the Salicylideneserinatecopper(II) Complex with β-Cyclodextrin: Characterization and Reactivity of the Inclusion Compound

The compound formed by the copper-Schiff base complex salicylideneserinatecopper(II), [Cu(sal-ser)(H2O)], interacting with -cyclodextrin was prepared, and characterized in the solid state by infrared, UV-visible and EPR spectroscopies, X- ray diffraction, and thermoanalytical techniques. The catalytic activity of this compound, [Cu(sal-ser)CD], in the decomposition of hydrogen peroxide, and in the dismutation of superoxide radicals was also verified, in comparison with the reactivity of the free complex, in aqueous solution. In both cases, a decreasing in the reaction rate was observed for the CD-containing compound. The results of structural characterization, in addition to the substantial differences observed in the catalytic activities of the compounds, are indicative of partial insertion of the copper complex in the cavity of the oligosaccharide.     

Nitric oxide interaction with cytochrome c' and its relevance to guanylate cyclase. Why does the iron histidine bond break?

Soluble guanylate cyclase (sGC), the mammalian receptor for nitric oxide (NO), is a heme protein with a histidine as the proximal ligand. Formation of a five-coordinate heme-NO complex with the associated Fe-His bond cleavage is believed to trigger a conformational change that activates the enzyme and transduces the NO signal. Cytochrome c' (cyt c') is a protobacteria heme protein that has several similarities with sGC, including the ability to form a five-coordinate NO adduct and the fact that it does not bind oxygen. Recent crystallographic characterization of cyt c' from Alcaligenes xylosoxidans (AXCP) has yielded the discovery that exogenous ligands are able to bind to the Fe center from either side of the porphyrin plane. In this paper, we explore the molecular basis of the NO interaction with AXCP using hybrid quantum-classical simulation techniques. Our results suggest that Fe-His bond breaking depends not only on the iron-histidine bond strength but also on the existence of a local minimum conformation of the protein with the histidine away from the iron. We also show that AXCP is a useful paradigm for NO interaction with heme proteins, particularly regarding the activation/deactivation mechanism of sGC. The results presented here fully support a recently proposed model of sGC activation in which NO is not only the iron ligand but also catalyzes the activation step.     

Polymerization and copolymerization studies on vinyl fluoride

The polymerization of vinyl fluoride has been studied in the temperature range of 0–50°C. with the aid of different types of initiators. Ziegler-Natta systems based on vanadyl acetylacetonate and AIR(OR)Cl compounds showed good activity. Enhanced reaction rates and higher polymerization degrees were achieved with boron alkyls (and, to a lesser degree, Cd, Zn, and Be alkyls) activated by oxygen. With either types of initiator, the main features and the kinetic parameters of the polymerization were determined. In all cases, the polymerization is considered to be of the free-radical type, though some properties (crystallinity, melting temperature) of the polymer are shown to be markedly improved over the previously described high-pressure polymer. This is chiefly ascribed to an improved degree of chemical regularity of the chains. The copolymerization of vinyl fluoride in the presence of the cited initiators was studied with a number of monomers. The values of the copolymerization parameters allow us to obtain Q (0.010 ± 0.005) and e (?0.8±0.2) values and to discuss the reactivity of vinyl fluoride in radical chain propagation.     

Synthesis of N,N-Dialkyl-N'-arylhydrazines via palladium-catalyzed N-arylation by using N,N-dialkylhydrazines/2LiCl adducts

[reaction: see text] The reaction of N,N-dialkylhydrazine/2LiCl adducts with aryl bromides in the presence of Pd(2)(dba)(3) as the palladium source, Xantphos or X-phos as the ligands, toluene as the solvent, and NaOBu-t as the base provides an efficient route to N,N-dialkyl-N'-arylhydrazines. Best results were obtained by using N,N-dialkylhydrazine/2LiCl adducts prepared in situ, omitting their isolation.     

UVA-ketoprofen-induced hemoglobin radicals detected by immuno-spin trapping

Ketoprofen (3-benzoyl-alpha-methylbenzeneacetic acid, KP) is a widely used nonsteroidal anti-inflammatory drug (NSAID) that causes both phototoxicity and photoallergy. Here, we investigated the formation of hemoglobin radicals, in both purified hemoglobin and red blood cells (RBC), induced by ultraviolet A (UVA)-KP by using "immuno-spin trapping," a novel approach that combines the specificity of spin trapping with the sensitivity of antigen-antibody interactions. The methemoglobin (metHb) radicals react covalently with 5,5-dimethyl-1-pyrroline N-oxide (DMPO) to form nitroxyl radical adducts that are oxidized to the corresponding nitrone adducts, which in turn are specifically recognized by antiserum against DMPO nitrone. We found that the formation of nitrone adducts in metHb depended on the UVA dose, the KP concentration and the presence of DMPO, as determined by enzyme-linked immunosorbent assay and Western blotting. Adduct formation decreased when irradiation was carried out in the presence of catalase or nitrogen, suggesting that H2O2 plays a key role in KP-UVA-induced metHb radical formation. KP in the dark did not generate metHb radical-derived nitrone adducts, whereas UVA alone resulted in the formation of metHb radical-derived nitrone adducts that increased with UVA dose from 4 to 10 J/cm2. However, KP (25 and 200 microM) plus UVA (4 and 10 J/cm2) resulted in a significant increase in the formation of metHb radical-derived nitrone adducts as compared with UVA or KP alone, indicating that KP photosensitized the production of the metHb radicals in the presence of UVA. In contrast, no metHb radical-derived nitrone adduct was detected in the absence of DMPO, even though KP and UVA were present. We also detected the hemoglobin radical formation in RBC as well as in hemolysates. The endogenous antioxidants and exogenous reduced glutathione inhibited the protein radical formation. These studies have shown that the immuno-spin-trapping technique can be used to detect radical damage in proteins as a result of photosensitizing reactions. The successful detection of protein radical formation caused by KP photosensitization could help further understand the photoallergic effect of this NSAID.     

Study of the conformation of γ-zeins in purified maize protein bodies by FTIR and NMR spectroscopy

The γ-zeins are a mixture of 16, 27, and 50-kDa polypeptides which are important in the formation and stabilization of protein bodies (PB). These organelles are used for deposition of zeins, the water-insoluble storage proteins in maize. The nature of the physical interaction between proteins in the assembly and stabilization of PB are fairly well known. It is suggested the repeated hexapeptide sequence (PPPVHL)₈ in the N-terminus is responsible for aggregation of the γ-zeins on the PB surface. Despite this importance, there is little information about the native conformation of γ-zeins. In this work, we have analyzed the secondary structures of γ-zeins in purified protein bodies from two maize cultivars, in the solid state, by FTIR and NMR spectroscopy. The results revealed that γ-zeins in their physiological state are comprise similar proportions of α-helix and β-sheet, 33 and 31% as determined by FTIR. It was not possible to state if the polyproline II (PPII) conformation is present in the solid-state structure of γ-zeins, as has been demonstrated for the hexapeptide in solution. Because of the similarity of the solid-state NMR spectra of γ and α-zeins in the α carbon region we attributed their contributions to the β-sheet structures rather than to the PPII conformation or a mixture of these extended structures.     

X-ray absorption spectroscopy to probe surface composition and surface deprotection in photoresist films

Near-edge X-ray absorption fine structure spectroscopy (NEXAFS) is utilized to provide insight into surface chemical effects in model photoresist films. First, NEXAFS was used to examine the resist/air interface including surface segregation of a photoacid generator (PAG) and the extent of surface deprotection in the film. The concentration of PAG at the resist-air interface was higher than the bulk concentration, which led to a faster deprotection rate at that interface. Second, a NEXAFS depth profiling technique was utilized to probe for compositional gradients in model resist line edge regions. In the model line edge region, the surface composition profile for the developed line edge was dependent on the post exposure bake time.