Linked Supramolecular Building Blocks for Enhanced Cluster Formation

Methylene‐bridged calix[4]arenes have emerged as extremely versatile ligand supports in the formation of new polymetallic clusters possessing fascinating magnetic properties. Metal ion binding rules established for this building block allow one to partially rationalise the complex assembly process. The ability to covalently link calix[4]arenes at the methylene bridge provides significantly improved control over the introduction of different metal centres to resulting cluster motifs. Clusters assembled from bis‐calix[4]arenes and transition metal ions or 3d‐4f combinations display characteristic features of the analogous calix[4]arene supported clusters, thereby demonstrating an enhanced and rational approach towards the targeted synthesis of complex and challenging structures.     

Facile Interchange of 3d and 4f Ions in Single‐Molecule Magnets: Stepwise Assembly of [Mn4], [Mn3Ln] and [Mn2Ln2] Cages within Calix[4]arene Scaffolds

The central Mn^II ions in a series of calix[4]arene‐stabilised butterflies can be sequentially replaced with Ln^III ions, maintaining the structural integrity of the molecule but transforming its magnetic properties. The replacement of Mn^II for Gd^III allows for the examination of the transferability of spin‐Hamiltonian parameters within the family as well as permitting their reliable determination. The introduction of the 4f ions results in weaker intramolecular magnetic exchange, an increase in the number of low‐lying excited states, and an increase in magnetisation relaxation, highlighting the importance of exchange over single‐ion anisotropy for the observation of SMM behaviour in this family of complexes. The presence of the [TM^II/III(TBC[4])(OH)(solvent)] metalloligand (TM=transition metal, TBC=p‐tBu‐calix[4]arene) suggests that magnetic calix[n]arene building blocks can be employed to encapsulate a range of different “guests” within structurally robust “hosts”.     

Scatter search for minimizing weighted tardiness in a single machine scheduling with setups

Single machine scheduling problems have many real-life applications and may be hard to solve due to the particular characteristics of some production environments. In this paper, we tackle the single machine scheduling problem with sequence-dependent setup times with the objective of minimizing the weighted tardiness. To solve this problem, we propose a scatter search algorithm which uses path relinking in its core. This algorithm is enhanced with some procedures to speed-up the neighbors’ evaluation and with some diversification and intensification techniques, the latter taking some elements from iterated local search. We conducted an experimental study across a well-known set of instances to analyze the contribution of each component to the overall performance of the algorithm, as well as to compare our proposal with the state-of-the-art metaheuristics, obtaining competitive results. We also propose a new benchmark with larger and more challenging instances and provide the first results for them.     

A bioinspired look at the glucosinolate metabolic pathway. Structural insights into the reaction of benzyl isothiocyanate and d-glucosamine

Through a well-established enzymatic transformation glucosinolates release reactive isothiocyanates that can undergo further metabolic pathways affording a plethora of reactive metabolites. This study explores in detail the reaction of benzyl isothiocyanate, which possesses antitumor activity as alkylating agent, with d-glucosamine, commonly employed in oral treatments against osteoarthritis and inflammation. Structures of the resulting products and their evolution have been assessed and compared with those involving d-glucose, reported previously. Chemical results suggest that clinical treatments with d-glucosamine could reduce the beneficial effects associated with diets based on glucosinolate-rich foods.     

Metabolomic analysis characterizes tissue specific indomethacin-induced metabolic perturbations of rats

In this study, the promising metabolomic approach integrating with ingenuity pathway analysis (IPA) was applied to characterize the tissue specific metabolic perturbation of rats that was induced by indomethacin. The selective pattern recognition analyses were applied to analyze global metabolic profiling of urine of rats treated by indomethacin at an acute dosage of reference that has been proven to induce tissue disorders in rats, evaluated throughout the time-course of -24-72 h. The results preliminarily revealed that modifications of amino acid metabolism, fatty acid metabolism and energetically associated metabolic pathways accounted for metabolic perturbation of the rats that was induced by indomethacin. Furthermore, IPA was applied to deeply analyze the biomarkers and their relations with the metabolic perturbations evidenced by pattern recognition analyses. Specific biochemical functions affected by indomethacin suggested that there is an important correlation of its effects in kidney and liver metabolism, based on the determined metabolites and their pathway-based analysis. The IPA correlation of the three major biomarkers, identified as creatinine, prostaglandin E2 and guanosine, suggested that the administration of indomethacin induced certain levels of toxicity in the kidneys and liver. The changes in the levels of biomarker metabolites allowed the phenotypical determination of the metabolic perturbations induced by indomethacin in a time-dependent manner.     

Hetero-Diels-Alder reaction of phosphinyl and phosphonyl nitroso alkenes with conjugated dienes: an aza-Cope rearrangement

Phosphorylated nitroso alkenes react with cyclic dienes such as cyclopentadiene or cyclohexadiene to afford hetero Diels-Alder-type cycloadducts where the nitroso alkene participates as dienophile component and the cyclic olefin acts as the 4π-electron (diene) system. Subsequent aza-Cope rearrangement affords highly functionalized 5,6-dihydro-4H-1,2-oxazines. Conversely, the reaction of TMS-substituted cyclopentadiene (dienophile) with nitroso alkenes as heterodienes leads directly to bicyclic 1,2-oxazines. Theoretical studies are in agreement with the experimental results and with the new aza-Cope rearrangement proposed.     

Vibrational spectra of double oxalates of the type M(I)2Cu(C2O4)(2)·2H2O (MI=Na+, K+, NH4+)

The infrared and Raman spectra of Na2Cu(C2O4)(2)·2H2O, K2Cu(C2O4)(2)·2H2O and (NH4)2Cu(C2O4)(2)·2H2O were recorded and briefly discussed on the basis of their structural peculiarities and by comparison with the vibrational spectra of other metallic oxalates.     

Probing vibrational wave packets in molecular excited states

A time-dependent theoretical method is used to describe a UV pump?CUV probe strategy to trace, at a femtosecond time scale, the motion of vibrational wave packets created in excited states of the hydrogen molecule by measuring single ionization probabilities. We use a spectral method to solve the time-dependent Schr?dinger equation in full dimensionality, including correlation and all electronic and vibrational degrees of freedom. A pump pulse initially creates a vibrational wave packet in the intermediate electronic excited states of $\hbox{H}_2$ . The frequency of the probe is chosen to ionize the target leaving the ion in a bound vibrational state. By varying the time delay between pulses, non-dissociative single ionization is enhanced or suppressed. Energy differential ionization probabilities are reported and compared with a model based on the Franck?CCondon approximation.     

On the stability and lifetime of GaO2+ in the gas phase

The electronic structure, stability, and lifetime of GaO²⁺ have been investigated using high-level ab initio calculations. The potential energy curves have been calculated at the CCSD(T)/aug-cc-pV5Z and at the MS-CASPT2/ANO-RCC levels of theory. Lifetimes were evaluated using the Exterior Complex Scaling (ECS) method and B-spline basis functions. Our calculations show that GaO²⁺ is a metastable species in the gas phase, since the diatomic dication, in its ground state, lies 97.1?kcal/mol above the Ga⁺ (¹S)?+?O⁺ (⁴S) dissociation limit. However, the energy barrier that has to be overcome to reach this limit is 3?kcal/mol high so that five vibrational resonances can be accommodated between the bottom of the well and the top of the barrier. The evaluated lifetimes vary from hundreds of femtoseconds to approximately 1?s, so at least two of them have long enough lifetimes (1?s and 91???s) to be detected using mass spectrometry techniques, in agreement with the experimental evidence. In the experiment (Fiser et al. in Eur J Mass Spectrom 15:315?C324, 2009), GaO²⁺ was observed for an ion flight time of about ~12???s through a magnetic-sector mass spectrometer and unambiguously identified by its isotopic abundance. Our results also show that isotopic effects on the resonances?? energies and on their lifetimes, when ⁷⁰Ga is replaced by ⁶⁹Ga or ⁷¹Ga, are very small (~0.1 and ~1%, respectively), reflecting the large mass of the system.