Electronic Structures of Reduced and Superreduced Ir-2(1,8-diisocyanomenthane)(4)(n+) Complexes

This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124). Additional support was provided by the Arnold and Mabel Beckman Foundation, the Ministry of Education of the Czech Republic (grant LD14129), and COST Actions CM1202 and CM1405

Evolutionary genetics of immunological supertypes reveals two faces of the Red Queen

Red Queen host-parasite co-evolution can drive adaptations of immune-genes by positive selection that erodes genetic variation (Red Queen Arms Race), or result in a balanced polymorphism (Red Queen Dynamics) and the long-term preservation of genetic variation (trans-species polymorphism). These two Red Queen processes are opposite extremes of the co-evolutionary spectrum. Here we show that both Red Queen processes can operate simultaneously, analyzing the Major Histocompatibility Complex (MHC) in guppies (Poecilia reticulata and P. obscura), and swamp guppies (Micropoecilia picta). Sub-functionalization of MHC alleles into “supertypes” explains how polymorphisms persist during rapid host-parasite co-evolution. Simulations show the maintenance of supertypes as balanced polymorphisms, consistent with Red Queen Dynamics, whereas alleles within supertypes are subject to positive selection in a Red Queen Arms Race. Building on the Divergent Allele Advantage hypothesis, we show that functional aspects of allelic diversity help to elucidate the evolution of polymorphic genes involved in Red Queen co-evolution

Tryptophan-Accelerated Electron Flow Through Proteins

Energy flow in biological structures often requires submillisecond charge transport over long molecular distances. Kinetics modeling suggests that charge-transfer rates can be greatly enhanced by multistep electron tunneling in which redox-active amino acid side chains act as intermediate donors or acceptors. We report transient optical and infrared spectroscopic experiments that quantify the extent to which an intervening tryptophan residue can facilitate electron transfer between distant metal redox centers in a mutant Pseudomonas aeruginosa azurin. CuI oxidation by a photoexcited ReI-diimine at position 124 on a histidine(124)-glycine(123)-tryptophan(122)-methionine(121) β strand occurs in a few nanoseconds, fully two orders of magnitude faster than documented for single-step electron tunneling at a 19 angstrom donor-acceptor distance

DNA Damage during G2 Phase Does Not Affect Cell Cycle Progression of the Green Alga Scenedesmus quadricauda

DNA damage is a threat to genomic integrity in all living organisms. Plants and green algae are particularly susceptible to DNA damage especially that caused by UV light, due to their light dependency for photosynthesis. For survival of a plant, and other eukaryotic cells, it is essential for an organism to continuously check the integrity of its genetic material and, when damaged, to repair it immediately. Cells therefore utilize a DNA damage response pathway that is responsible for sensing, reacting to and repairing damaged DNA. We have studied the effect of 5-fluorodeoxyuridine, zeocin, caffeine and combinations of these on the cell cycle of the green alga Scenedesmus quadricauda. The cells delayed S phase and underwent a permanent G2 phase block if DNA metabolism was affected prior to S phase; the G2 phase block imposed by zeocin was partially abolished by caffeine. No cell cycle block was observed if the treatment with zeocin occurred in G2 phase and the cells divided normally. CDKA and CDKB kinases regulate mitosis in S. quadricauda; their kinase activities were inhibited by Wee1. CDKA, CDKB protein levels were stabilized in the presence of zeocin. In contrast, the protein level of Wee1 was unaffected by DNA perturbing treatments. Wee1 therefore does not appear to be involved in the DNA damage response in S. quadricauda. Our results imply a specific reaction to DNA damage in S. quadricauda, with no cell cycle arrest, after experiencing DNA damage during G2 phase

Database-driven High-Throughput Calculations and Machine Learning Models for Materials Design

This paper reviews past and ongoing efforts in using high-throughput ab-inito calculations in combination with machine learning models for materials design. The primary focus is on bulk materials, i.e., materials with fixed, ordered, crystal structures, although the methods naturally extend into more complicated configurations. Efficient and robust computational methods, computational power, and reliable methods for automated database-driven high-throughput computation are combined to produce high-quality data sets. This data can be used to train machine learning models for predicting the stability of bulk materials and their properties. The underlying computational methods and the tools for automated calculations are discussed in some detail. Various machine learning models and, in particular, descriptors for general use in materials design are also covered.Comment: 19 pages, 2 figure

Recent advances in the study of the initiation of energetic materials rusing characteristics of their thermal decomposition. Part I, Cyclic nitramines

Arrhenius parameters, Ea and log A, of 17 cyclic nitramines, derived from the Russian vacuum manometric method (SMM) and compatible thermoanalytical methods, have been used in this study. The detonation velocity, D, at maximum theoretical crystal density, of the nitramines in this study was taken as a characteristic of their detonation. On the basis of known relationships between their Ea and D2 values (modified Evans-Polanyi-Semenov equation), the specific influence of some physicochemical properties on their thermal decomposition was shown. A new logarithmic relationship was found between the rate constant k, of the unimolecular thermal decomposition of the nitramines studied at 230 °C, and their D values. A fundamental characteristic of this new relationship rests on the equivalency of the primary fission processes in the low-temperature thermal decomposition and on the detonation initiation of the nitramines under study. Both these relationships confirm the problems encountered in the kinetic specification of the thermal decomposition of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12hexaazaisowurtzitane (HNIW, CL-20) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX). These problems, and also the possible influence of the pre-decomposition states on the thermal decomposition of the nitramines studied, are discussed