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The present work investigates alumino-phosphate glasses from Li2O–BaO–Al2O3–La2O3–P2O5 system containing Sm3+ and Eu3+ ions, prepared by two different ways: a wet raw materials mixing route followed by evaporation and melt-quenching, and by remelting of shards. The linear thermal expansion coefficient measured by dilatometry is identical for both rare-earth-doped phosphate glasses. Comparatively to undoped phosphate glass the linear thermal expansion coefficient increases with 2 × 10−7 K−1 when dopants are added. The characteristic temperatures very slowly decrease but can be considered constant with atomic weight, atomic number and f electrons number of the doping ions in the case of Tg (vitreous transition temperature) and Tsr (high annealing temperature) but slowly increase in the case of Tir (low annealing temperature–strain point) and very slowly increase, being practically constant in the case of TD (dilatometric softening temperature). Comparatively to undoped phosphate glass the characteristic temperatures of Sm and Eu-doped glasses present lower values. The higher values of electrical conductance for both doped glasses, comparatively to usual soda-lime-silicate glass, indicate a slightly reduced stability against water. The viscosity measurements, showed a quasi-linear variation with temperature the mean square deviation (R2) being ranged between 0.872% and 0.996%. The viscosity of doped glasses comparatively to the undoped one is lower at the same temperature. Thermogravimetric analysis did not show notable mass change for any of doped samples. DSC curves for both rare-earth-doped phosphate glasses, as bulk and powdered samples, showed Tg values in the range 435–450 °C. Bulk samples exhibited a very weak exothermic peak at about 685 °C, while powdered samples showed two weak exothermic peaks at about 555 °C and 685 °C due to devitrification of the glasses. Using designed melting and annealing programs, the doped glasses were improved regarding bubbles and cords content and strain elimination.

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The ongoing German energy transition causes a higher demand for reliable energy storage in the future. This increasing demand for sustainable, cheap, safe and efficient energy storage systems has caused a stronger public debate about the potential benefits of grid battery storage according to sustainability. This circumstance led to the preposition that there is a need for the development of a proper ex-ante assessment strategy to support technology uptake. The developed approach represents a framework for prospective system analysis (PSA) using the heuristics of constructive technology assessment to identify consequences, application possibilities or threats in the technological trajectory of grid battery storage. Within this framework PSA is used to quantitatively assess economic, environmental and social aspects along the entire life cycle of electrochemical energy storage technologies in order to identify hotspots according to sustainability. The Analytic Hierarchic Process (AHP) supports multiple methods in data collection and enables the analyst to combine results from PSA with qualitative actor notions about technology according to the “world” where it is embodied. In this sense AHP enables to achieve an optimum construct of technology from a stakeholder view point. The developed approach represents an efficient research strategy to shape technology in a sustainable way in frame of „Responsible Research and Innovation“.

Tumor-infiltrating lymphocytes (TILs) are important prognostic factors in cancer progression and key players in cancer immunotherapy. Although γδ T lymphocytes can target a diversity of tumor cell types, their clinical manipulation is hampered by our limited knowledge of the molecular cues that determine γδ T cell migration toward tumors in vivo. In this study we set out to identify the chemotactic signals that orchestrate tumor infiltration by γδ T cells. We have used the preclinical transplantable B16 melanoma model to profile chemokines in tumor lesions and assess their impact on γδ TIL recruitment in vivo. We show that the inflammatory chemokine CCL2 and its receptor CCR2 are necessary for the accumulation of γδ TILs in B16 lesions, where they produce IFN-γ and display potent cytotoxic functions. Moreover, CCL2 directed γδ T cell migration in vitro toward tumor extracts, which was abrogated by anti-CCL2 neutralizing Abs. Strikingly, the lack of γδ TILs in TCRδ-deficient but also in CCR2-deficient mice enhanced tumor growth in vivo, thus revealing an unanticipated protective role for CCR2/CCL2 through the recruitment of γδ T cells. Importantly, we demonstrate that human Vδ1 T cells, but not their Vδ2 counterparts, express CCR2 and migrate to CCL2, whose expression is strongly deregulated in multiple human tumors of diverse origin, such as lung, prostate, liver, or breast cancer. This work identifies a novel protective role for CCL2/CCR2 in the tumor microenvironment, while opening new perspectives for modulation of human Vδ1 T cells in cancer immunotherapy.

The preferential binding of anions and cations in aqueous solutions of the ionic liquids (ILs) 1-butyl- 3-methylimidazolium ([C₄mim]⁺) and 1-ethyl-3-methylimidazolium ([C₂mim]⁺) chloride and dicyanamide (dca^-) with the small alpha-helical protein Im7 was investigated using a combination of differential scanning calorimetry, NMR spectroscopy and molecular dynamics (MD) simulations. Our results show that direct ion interactions are crucial to understand the effects of ILs on the stability of proteins and that an anion effect is dominant. We show that the binding of weakly hydrated anions to positively charged or polar residues leads to the partial dehydration of the backbone groups, and is critical to control stability, explaining why dca^- is more denaturing than Cl^-. Direct cation–protein interactions also mediate stability; cation size and hydrophobicity are relevant to account for destabilisation as shown by the effect of [C₄mim]⁺ compared to [C₂mim]⁺. The specificity in the interaction of IL ions with protein residues established by weak favourable interactions is confirmed by NMR chemical shift perturbation, amide hydrogen exchange data and MD simulations. Differences in specificity are due to the balance of interaction established between ion pairs and ion-solvent that determine the type of residues affected. When the interaction of both cation and anion with the protein is strong the net result is similar to a non-specific interaction, leading ultimately to unfolding. Since the nature of the ions is a determinant of the level of interaction with the protein towards denaturation or stabilisation, ILs offer a unique possibility to modulate protein stabilisation or even folding events.

The spontaneous two-photon emission in hydrogenlike ions is investigated within the framework of second- order perturbation theory and Dirac’s equation. Special attention is paid to the angular correlation of the emitted photons as well as to the degree of linear polarization of one of the two photons, if the second is just observed under arbitrary angles. Expressions for the angular correlation and the degree of linear polarization are expanded in powers of cosine functions of the two-photon opening angle, whose coefficients depend on the atomic number and the energy sharing of the emitted photons. The effects of including higher (electric and magnetic) multipoles upon the emitted photon pairs beyond the electric-dipole approximation are also discussed. Calculations of the coefficients are performed for the transitions 2s1/2 → 1s1/2, 3d3/2 → 1s1/2, and 3d5/2 → 1s1/2, along the entire hydrogen isoelectronic sequence (1

O sector da construção enfrenta actualmente um momento de crise na sua produção. Esta situação tem levado as empresas nacionais a apostar mais no mercado da reabilitação de edifícios. A acrescentar a esta mudança de mercado alvo, o ambiente conturbado que envolve as empresas de construção tem também estimulado, pelo menos as mais competitivas, a implementarem acções que conduzam à melhoria contínua da sua produtividade.
A industrialização do sector, através da utilização da pré-fabricação, mostra-se como uma possível solução para atingir esta melhoria desejada, considerando as significativas vantagens que a aplicação deste tipo de soluções introduz numa obra.
Existem contudo, ainda algumas barreiras no sector da construção que levam a uma reduzida utilização de
soluções de pré-fabricação, sendo a falta de conhecimento dos intervenientes das variedades de tecnologias existentes no mercado e em desenvolvimento, o principal obstáculo à sua adopção.
O presente artigo pretende, tornar evidentes as vantagens que esta tecnologia construtiva traz para o processo de construção e reabilitação, tanto ao nível de eficiência económica como ao nível dos seus benefícios ambientais e sociais, bem como, evidenciar as possibilidades de aplicação de sistemas de pré-fabricação existentes e em desenvolvimento, em detrimento das tecnologias construtivas convencionais, para diversas acções de
reabilitação habitualmente realizadas num edifício.

Cytochromes c7 are periplasmic triheme proteins that have been reported exclusively in δ-proteobacteria. The structures of five triheme cytochromes identified in Geobacter sulfurreducens and one in Desulfuromonas acetoxidans have been determined. In addition to the hemes and axial histidines, a single aromatic residue is conserved in all these proteins - phenylalanine 15 (F15). PpcA is a member of the G. sulfurreducens cytochrome c7 family that performs electron/proton energy transduction in addition to electron transfer that leads to the reduction of extracellular electron acceptors. For the first time we probed the role of the F15 residue in the PpcA functional mechanism, by replacing this residue with the aliphatic leucine by site-directed mutagenesis. The analysis of NMR spectra of both oxidized and reduced forms showed that the heme core and the overall fold of the mutated protein were not affected. However, the analysis of 1H-15N heteronuclear single quantum coherence NMR spectra evidenced local rearrangements in the α-helix placed between hemes I and III that lead to structural readjustments in the orientation of heme axial ligands. The detailed thermodynamic characterization of F15L mutant revealed that the reduction potentials are more negative and the redox-Bohr effect is decreased. The redox potential of heme III is most affected. It is of interest that the mutation in F15, located between hemes I and III in PpcA, changes the characteristics of the two hemes differently. Altogether, these modifications disrupt the balance of the global network of cooperativities, preventing the F15L mutant protein from performing a concerted electron/proton transfer.

Protein phosphorylation is a complex and highly dynamic process involved in numerous biological events. Abnormal phosphorylation is one of the underlying mechanisms for the development of cancer and metabolic disorders. The identification and absolute quantification of specific phospho-signatures can help elucidate protein functions in signaling pathways and facilitate the development of new and personalized diagnostic and therapeutic tools. This review presents a variety of strategies currently utilized for the enrichment of phosphorylated proteins and peptides before mass spectrometry analysis during proteomic studies. The investigation of specific affinity reagents, allied to the integration of different enrichment processes, is triggering the development of more selective, rapid and cost-effective high-throughput automated platforms.