Unveiling the photophysics of thiourea from CASPT2/CASSCF potential energy surfaces and singlet/triplet excited state molecular dynamics simulations

This work describes the decay mechanism of photoexcited thiourea, both in gas phase and in solution, from the information inferred from the topography of the excited and ground state potential energy surfaces and mixed singlet/triplet quantum classical molecular dynamics simulations. Our gas phase results reveal T1/S0 intersystem crossing as the dominant (49%) intrinsic decay channel to the ground state, which reaches a population of 0.28 at the final time of our simulations (10 ps). Population of the T1, would occur after internal conversion to the S1 from the spectroscopic S2 electronic state, followed by S1->T2 intersystem crossing and T2->T1 internal conversion processes. Minor decay channels occurring exclusively along the singlet manifold, i.e. S2->S0 (33%) and S1->S0 (18%), were also observed to play a role in the relaxation of photoexcited thiourea in the gas phase. The explicit incorporation of water-thiourea interactions in our simulations was found to provoke a very significant delay in the decay to the ground state of the system, with no transitions to the S0 being registered during the first 10 ps of our simulations. Intermolecular vibrational energy redistribution and explicit hydrogen bond interaction established between water molecules and the NH2 group of thiourea were found to structurally or energetically hamper the access to the intersystem crossing or internal conversion funnels with the ground state

Casimir Energy for concentric δ\delta-δ′\delta' spheres

We study the vacuum interaction of a scalar field and two concentric spheres defined by a singular potential on their surfaces. The potential is a linear combination of the Dirac-$\delta$ and its derivative. The presence of the delta prime term in the potential causes that it behaves differently when it is seen from the inside or from the outside of the sphere. We study different cases for positive and negative values of the delta prime coupling, keeping positive the coupling of the delta. As a consequence, we find regions in the space of couplings, where the energy is positive, negative or zero. Moreover, the sign of the $\delta'$ couplings cause different behavior on the value of the Casimir energy for different values of the radii. This potential gives rise to general boundary conditions with limiting cases defining Dirichlet and Robin boundary conditions what allows us to simulate purely electric o purely magnetic spheres.Comment: 9 pages, 8 figures We are submitting this manuscript for publication in Physical Review

Excited state dynamics of some nonsteroidal anti-inflammatory drugs: a surface-hopping investigation

Here we present a computational investigation of the excited state dynamics of 5 different active medical substances (aspirin, ibuprofen, carprofen, suprofen, indomethacin) which belong to the family of nonsteroidal anti-inflammatory drugs (NSAIDs). The nonadiabatic dynamics simulations were performed using the surface hopping method, with electronic energies and couplings evaluated on the fly in a semiempirical framework. For aspirin, the solvent decay dynamics was also considered by inserting it in a cluster of water molecules, following a QM/MM scheme. A quite diverse behavior was observed for the systems considered, going from fast deactivation to the ground state (aspirin and ibuprofen), to ultrafast intersystem crossing to the triplet manifold (carprofen and suprofen), or to the generation of long lived S1 states (indomethacin). To our knowledge, this is the first computational study of the photodynamics of these NSAIDs

Can grit be taught? Lessons from a nationwide field experiment with middle-school students

We study whether a particular socio-emotional skill - grit (the ability to sustain effort and interest towards long-term goals) - can be cultivated through a large-scale program, and how this affects student learning. Using a randomized control trial, we evaluate the first nationwide implementation of a low-cost intervention designed to foster grit and self-regulation among sixth and seventh-grade students in primary schools in North Macedonia (about 33,000 students across 350 schools). The results of this interventions are mixed. Exposed students report improvements in self-regulation, in particular the perseverance-of-effort facet of grit, relative to students in a control condition. Impacts on students are larger when both students and teachers are exposed to the curriculum than when only students are treated. For disadvantaged students, we also find positive impacts on grade point averages, with gains of up to 28 percent of a standard deviation one-year post-treatment. However, while this intervention made students more perseverant and industrious, it reduced the consistency-of-interest facet of grit. This means that exposed students are less able to maintain consistent interests for long periods

Experimental evaluation of ecological principles to understand and modulate the outcome of bacterial strain competition in gut microbiomes

It is unclear if coexistence theory can be applied to gut microbiomes to understand their characteristics and modulate their composition. Through experiments in gnotobiotic mice with complex microbiomes, we demonstrated that strains of Akkermansia muciniphila and Bacteroides vulgatus could only be established if microbiomes were devoid of these species. Strains of A. muciniphila showed strict competitive exclusion, while B. vulgatus strains coexisted but populations were still influenced by competitive interactions. These differences in competitive behavior were reflective of genomic variation within the two species, indicating considerable niche overlap for A. muciniphila strains and a broader niche space for B. vulgatus strains. Priority effects were detected for both species as strains’ competitive fitness increased when colonizing first, which resulted in stable persistence of the A. muciniphila strain colonizing first and competitive exclusion of the strain arriving second. Based on these observations, we devised a subtractive strategy for A. muciniphila using antibiotics and showed that a strain from an assembled community can be stably replaced by another strain. By demonstrating that competitive outcomes in gut ecosystems depend on niche differences and are historically contingent, our study provides novel information to explain the ecological characteristics of gut microbiomes and a basis for their modulation

Racism: A Teenagers\u27 Perspective Results of Preliminary Research from Madrid, Spain

In mid-June, 2005, the members of the INTER Center received a collaboration proposal from FETE-UGT8, with the objective of carrying out a brief exploratory study on the perceptions and experiences that young people and adolescents, mainly immigrants, have concerning possible experiences of discrimination and racism in their immediate surroundings. The initial objectives of the project were expanded due to the dynamics of the project itself. New focuses of attention and social, educational and personal dynamics, which can condition to a certain extent the experiences that immigrant adolescents undergo, were detected. The project initially consisted of a series of interviews with adolescents between 12 and 18 years of age. A total of 20 interviews were carried out, some of them group interviews. We consider this project focus, although positive, to be limited, and we think that it would have been necessary to broaden the sample and consider other people in the young people’s social and family environment (family members, friends, classmates, professors, all of them of different origins, including the host country)

Scenarios of Electromobility. Cross ferilisation and Dissemination of Best Practices and Researches within EU Policies Webinar proceedings

La pubblicazione riporta gli esiti del webinar incentrato sull'user center design dei veicoli elettrici, delle loro infrastrutture di ricarica e sulle sperimentazioni dei veicoli elettrici leggeri nei sistemi di trasporto urbano di Torino e Venaria Reale (IT), Villach (Austria) e Calvià (Spagna). La pubblicazione e il seminario sono parte del progetto STEVE, finanziato dal programma europeo Horizon2020, e incentrato sulla sperimentazione di modelli di mobilità elettrica leggera nelle aree urbane. Il progetto ha coinvolto città, piccole e medie imprese e università di sette paesi europei. Urban Lab ha collaborato con la Città di Torino a delineare le raccomandazioni rivolte ai decision makers in materia di pianificazione della mobilità urbana, emerse dai risultati dei tre anni di progetto

Association of Candidate Gene Polymorphisms With Chronic Kidney Disease: Results of a Case-Control Analysis in the Nefrona Cohort

Chronic kidney disease (CKD) is a major risk factor for end-stage renal disease, cardiovascular disease and premature death. Despite classical clinical risk factors for CKD and some genetic risk factors have been identified, the residual risk observed in prediction models is still high. Therefore, new risk factors need to be identified in order to better predict the risk of CKD in the population. Here, we analyzed the genetic association of 79 SNPs of proteins associated with mineral metabolism disturbances with CKD in a cohort that includes 2, 445 CKD cases and 559 controls. Genotyping was performed with matrix assisted laser desorption ionizationtime of flight mass spectrometry. We used logistic regression models considering different genetic inheritance models to assess the association of the SNPs with the prevalence of CKD, adjusting for known risk factors. Eight SNPs (rs1126616, rs35068180, rs2238135, rs1800247, rs385564, rs4236, rs2248359, and rs1564858) were associated with CKD even after adjusting by sex, age and race. A model containing five of these SNPs (rs1126616, rs35068180, rs1800247, rs4236, and rs2248359), diabetes and hypertension showed better performance than models considering only clinical risk factors, significantly increasing the area under the curve of the model without polymorphisms. Furthermore, one of the SNPs (the rs2248359) showed an interaction with hypertension, being the risk genotype affecting only hypertensive patients. We conclude that 5 SNPs related to proteins implicated in mineral metabolism disturbances (Osteopontin, osteocalcin, matrix gla protein, matrix metalloprotease 3 and 24 hydroxylase) are associated to an increased risk of suffering CKD

Comparison of seven prognostic tools to identify low-risk pulmonary embolism in patients aged <50 years

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