The role of electronic triplets and high-lying singlet states in the deactivation mechanism of the parent BODIPY: An ADC(2) and CASPT2 study

The potential tunability of the spectroscopic properties of the BODIPY parent dye by suitable functionalization makes it attractive for a number of applications. Unfortunately, its strong fluorescence against minor intersystem crossing to the triplet states prevents its application in photodynamic therapy. With the perspective of designing BODIPY derivatives with enhanced intersystem crossing, the goal of this work is two-fold: (i) investigate the main deactivation channels of the parent BODIPY following irradiation, paying particular attention to the accessibility of the triplet state potential energy surfaces, as well as the non-radiative pathways involving the second brightest more stable singlet electronic state, S2, and (ii) evaluate the performance of the computationally efficient second order algebraic-diagrammatic construction scheme for the polarization propagator, (ADC(2)) against the complete active space second-order perturbation theory (CASPT2) method. Three singlet/triplet crossings were found, all of them with small spin-orbit couplings, being the S1/T2 crossing the most plausible for the observed intersystem crossing yield. Methodologically, it is found that the ADC(2) method qualitatively reproduces the landscape of the potential energy profiles for the photophysical processes investigated; however, it systematically underestimates the energies of the stationary points and crossings of the same and different multiplicity, with the largest discrepancies found at S1/S0 crossing points. Our CASPT2 results provide a comprehensive picture of the landscape of the excited state potential energy surfaces of the parent BODIPY that might serve as a basis for the rational design of photosensitizers with a particular photophysical profileThis work has been supported by the Project CTQ2015-63997- C2 of the Ministerio de Economía y Competitividad of Spain. I.C. gratefully acknowledges the “Ramón y Cajal” program of the Ministerio de Economía y Competitividad of Spain. M.D.V. thanks the Marie Curie Actions, within the Innovative Training Network-European Join Doctorate in Theoretical Chemistry and Computational Modelling TCCM-ITN-EJD-642294, for financial suppor

6-Deoxyhexoses froml-Rhamnose in the Search for Inducers of the Rhamnose Operon: Synergy of Chemistry and Biotechnology

In the search for alternative non‐metabolizable inducers in the l ‐rhamnose promoter system, the synthesis of fifteen 6‐deoxyhexoses from l ‐rhamnose demonstrates the value of synergy between biotechnology and chemistry. The readily available 2,3‐acetonide of rhamnonolactone allows inversion of configuration at C4 and/or C5 of rhamnose to give 6‐deoxy‐d ‐allose, 6‐deoxy‐d ‐gulose and 6‐deoxy‐l ‐talose. Highly crystalline 3,5‐benzylidene rhamnonolactone gives easy access to l ‐quinovose (6‐deoxy‐l ‐glucose), l ‐olivose and rhamnose analogue with C2 azido, amino and acetamido substituents. Electrophilic fluorination of rhamnal gives a mixture of 2‐deoxy‐2‐fluoro‐l ‐rhamnose and 2‐deoxy‐2‐fluoro‐l ‐quinovose. Biotechnology provides access to 6‐deoxy‐l ‐altrose and 1‐deoxy‐l ‐fructose

On Bootstrap Percolation in Living Neural Networks

Recent experimental studies of living neural networks reveal that their global activation induced by electrical stimulation can be explained using the concept of bootstrap percolation on a directed random network. The experiment consists in activating externally an initial random fraction of the neurons and observe the process of firing until its equilibrium. The final portion of neurons that are active depends in a non linear way on the initial fraction. The main result of this paper is a theorem which enables us to find the asymptotic of final proportion of the fired neurons in the case of random directed graphs with given node degrees as the model for interacting network. This gives a rigorous mathematical proof of a phenomena observed by physicists in neural networks

Finding long cycles in graphs

We analyze the problem of discovering long cycles inside a graph. We propose and test two algorithms for this task. The first one is based on recent advances in statistical mechanics and relies on a message passing procedure. The second follows a more standard Monte Carlo Markov Chain strategy. Special attention is devoted to Hamiltonian cycles of (non-regular) random graphs of minimal connectivity equal to three

Statistical Mechanics of maximal independent sets

The graph theoretic concept of maximal independent set arises in several practical problems in computer science as well as in game theory. A maximal independent set is defined by the set of occupied nodes that satisfy some packing and covering constraints. It is known that finding minimum and maximum-density maximal independent sets are hard optimization problems. In this paper, we use cavity method of statistical physics and Monte Carlo simulations to study the corresponding constraint satisfaction problem on random graphs. We obtain the entropy of maximal independent sets within the replica symmetric and one-step replica symmetry breaking frameworks, shedding light on the metric structure of the landscape of solutions and suggesting a class of possible algorithms. This is of particular relevance for the application to the study of strategic interactions in social and economic networks, where maximal independent sets correspond to pure Nash equilibria of a graphical game of public goods allocation

The early evolution of the H-free process

The H-free process, for some fixed graph H, is the random graph process defined by starting with an empty graph on n vertices and then adding edges one at a time, chosen uniformly at random subject to the constraint that no H subgraph is formed. Let G be the random maximal H-free graph obtained at the end of the process. When H is strictly 2-balanced, we show that for some c>0, with high probability as $n \to \infty$, the minimum degree in G is at least $cn^{1-(v_H-2)/(e_H-1)}(\log n)^{1/(e_H-1)}$. This gives new lower bounds for the Tur\'an numbers of certain bipartite graphs, such as the complete bipartite graphs $K_{r,r}$ with $r \ge 5$. When H is a complete graph $K_s$ with $s \ge 5$ we show that for some C>0, with high probability the independence number of G is at most $Cn^{2/(s+1)}(\log n)^{1-1/(e_H-1)}$. This gives new lower bounds for Ramsey numbers R(s,t) for fixed $s \ge 5$ and t large. We also obtain new bounds for the independence number of G for other graphs H, including the case when H is a cycle. Our proofs use the differential equations method for random graph processes to analyse the evolution of the process, and give further information about the structure of the graphs obtained, including asymptotic formulae for a broad class of subgraph extension variables.Comment: 36 page

Synthetic Chemical Inducers and Genetic Decoupling Enable Orthogonal Control of the rhaBAD Promoter

External control of gene expression is crucial in synthetic biology and biotechnology research and applications, and is commonly achieved using inducible promoter systems. The E. coli rhamnose-inducible rhaBAD promoter has properties superior to more commonly used inducible expression systems, but is marred by transient expression caused by degradation of the native inducer, l-rhamnose. To address this problem, 35 analogues of l-rhamnose were screened for induction of the rhaBAD promoter, but no strong inducers were identified. In the native configuration, an inducer must bind and activate two transcriptional activators, RhaR and RhaS. Therefore, the expression system was reconfigured to decouple the rhaBAD promoter from the native rhaSR regulatory cascade so that candidate inducers need only activate the terminal transcription factor RhaS. Rescreening the 35 compounds using the modified rhaBAD expression system revealed several promising inducers. These were characterized further to determine the strength, kinetics, and concentration-dependence of induction; whether the inducer was used as a carbon source by E. coli; and the modality (distribution) of induction among populations of cells. l-Mannose was found to be the most useful orthogonal inducer, providing an even greater range of induction than the native inducer l-rhamnose, and crucially, allowing sustained induction instead of transient induction. These findings address the key limitation of the rhaBAD expression system and suggest it may now be the most suitable system for many applications

Cooperative Behavior of Kinetically Constrained Lattice Gas Models of Glassy Dynamics

Kinetically constrained lattice models of glasses introduced by Kob and Andersen (KA) are analyzed. It is proved that only two behaviors are possible on hypercubic lattices: either ergodicity at all densities or trivial non-ergodicity, depending on the constraint parameter and the dimensionality. But in the ergodic cases, the dynamics is shown to be intrinsically cooperative at high densities giving rise to glassy dynamics as observed in simulations. The cooperativity is characterized by two length scales whose behavior controls finite-size effects: these are essential for interpreting simulations. In contrast to hypercubic lattices, on Bethe lattices KA models undergo a dynamical (jamming) phase transition at a critical density: this is characterized by diverging time and length scales and a discontinuous jump in the long-time limit of the density autocorrelation function. By analyzing generalized Bethe lattices (with loops) that interpolate between hypercubic lattices and standard Bethe lattices, the crossover between the dynamical transition that exists on these lattices and its absence in the hypercubic lattice limit is explored. Contact with earlier results are made via analysis of the related Fredrickson-Andersen models, followed by brief discussions of universality, of other approaches to glass transitions, and of some issues relevant for experiments.Comment: 59 page

A double-sided, shield-less stave prototype for the ATLAS upgrade strip tracker for the high luminosity LHC

A detailed description of the integration structures for the barrel region of the silicon strips tracker of the ATLAS Phase-II upgrade for the upgrade of the Large Hadron Collider, the so-called High Luminosity LHC (HL-LHC), is presented. This paper focuses on one of the latest demonstrator prototypes recently assembled, with numerous unique features. It consists of a shortened, shield-less, and double sided stave, with two candidate power distributions implemented. Thermal and electrical performances of the prototype are presented, as well as a description of the assembly procedures and tools

A double-sided silicon micro-strip super-module for the ATLAS inner detector upgrade in the high-luminosity LHC

The ATLAS experiment is a general purpose detector aiming to fully exploit the discovery potential of the Large Hadron Collider (LHC) at CERN. It is foreseen that after several years of successful data-taking, the LHC physics programme will be extended in the so-called High-Luminosity LHC, where the instantaneous luminosity will be increased up to 5 × 1034 cm−2 s−1. For ATLAS, an upgrade scenario will imply the complete replacement of its internal tracker, as the existing detector will not provide the required performance due to the cumulated radiation damage and the increase in the detector occupancy. The current baseline layout for the new ATLAS tracker is an all-silicon-based detector, with pixel sensors in the inner layers and silicon micro-strip detectors at intermediate and outer radii. The super-module is an integration concept proposed for the strip region of the future ATLAS tracker, where double-sided stereo silicon micro-strip modules are assembled into a low-mass local support structure. An electrical super-module prototype for eight double-sided strip modules has been constructed. The aim is to exercise the multi-module readout chain and to investigate the noise performance of such a system. In this paper, the main components of the current super-module prototype are described and its electrical performance is presented in detail