First joint observations of space weather events over Mexico

Abstract. The Mexican Space Weather Service (SCiESMEX in Spanish) and National Space Weather Laboratory (LANCE in Spanish) were organized in 2014 and in 2016, respectively, to provide space weather monitoring and alerts, as well as scientific research in Mexico. In this work, we presenttheresultsofthefirstjointobservationsoftwoevents (22 June and 29 September 2015) with our local network of instruments and their related products. This network includes the MEXART radio telescope (solar flare and radio burst), the Compact Astronomical Low-frequency, Low-cost Instrument for Spectroscopy in Transportable Observatories (CALLISTO)attheMEXARTstation(solarradioburst),the Mexico City Cosmic Ray Observatory (cosmic ray fluxes), GPS receiver networks (ionospheric disturbances), and the Teoloyucan Geomagnetic Observatory (geomagnetic field). The observations show that we detected significant space weather effects over the Mexican territory: geomagnetic and ionospheric disturbances (22 June 2015), variations in cosmicrayfluxes,andalsoradiocommunications’interferences (29September2015).Theeffectsoftheseperturbationswere registered,forthefirsttime,usingspaceweatherproductsby SCiESMEX:totalelectroncontent(TEC)maps,regionalgeomagneticindexKmex,radiospectrographsoflowfrequency, and cosmic ray fluxes. These results prove the importance of monitoring space weather phenomena in the region and the need to strengthening the instrumentation network

BLUF Domain Function Does Not Require a Metastable Radical Intermediate State

BLUF (blue light using flavin) domain proteins are an important family of blue light-sensing proteins which control a wide variety of functions in cells. The primary light-activated step in the BLUF domain is not yet established. A number of experimental and theoretical studies points to a role for photoinduced electron transfer (PET) between a highly conserved tyrosine and the flavin chromophore to form a radical intermediate state. Here we investigate the role of PET in three different BLUF proteins, using ultrafast broadband transient infrared spectroscopy. We characterize and identify infrared active marker modes for excited and ground state species and use them to record photochemical dynamics in the proteins. We also generate mutants which unambiguously show PET and, through isotope labeling of the protein and the chromophore, are able to assign modes characteristic of both flavin and protein radical states. We find that these radical intermediates are not observed in two of the three BLUF domains studied, casting doubt on the importance of the formation of a population of radical intermediates in the BLUF photocycle. Further, unnatural amino acid mutagenesis is used to replace the conserved tyrosine with fluorotyrosines, thus modifying the driving force for the proposed electron transfer reaction; the rate changes observed are also not consistent with a PET mechanism. Thus, while intermediates of PET reactions can be observed in BLUF proteins they are not correlated with photoactivity, suggesting that radical intermediates are not central to their operation. Alternative nonradical pathways including a keto–enol tautomerization induced by electronic excitation of the flavin ring are considered

Hetero-cycloreversions Mediated by Photoinduced Electron Transfer

[EN] Discovered more than eight decades ago, the Diels-Alder (DA) cycloaddition (CA) remains one of the most versatile tools in synthetic organic chemistry. Hetero-DA processes are powerful methods for the synthesis of densely functionalized six-membered heterocycles, ubiquitous substructures found in natural products and bioactive compounds. These reactions frequently employ azadienes and oxadienes, but only a few groups have reported DA processes with thiadienes. The electron transfer (ET) version of the DA reaction, though less investigated, has emerged as a subject of increasing interest. In the last two decades, researchers have paid closer attention to radical ionic hetero-cycloreversions, mainly in connection with their possible involvement in the repair of pyrimidine(6-4)pyrimidone photolesions in DNA by photolyases. In biological systems, these reactions likely occur through a reductive photosensitization mechanism. In addition, photooxidation can lead to cycloreversion (CR) reactions, and researchers can exploit this strategy for DNA repair therapies. In this Account, we discuss electron-transfer (ET) mediated hetero-CR reactions. We focus on the oxidative and reductive ET splitting of oxetanes, azetidines, and thietanes. Photoinduced electron transfer facilitates the splitting of a variety of four-membered heterocycles. In this context, researchers have commonly examined oxetanes, both experimentally and theoretically. Although a few studies have reported the cycloreversion of azetidines and thietanes carried out under electron transfer conditions, the number of examples remains limited. In general, the cleavage of the ionized four-membered rings appears to occur via a nonconcerted two-step mechanism. The trapping of the intermediate 1,4-radical ions and transient absorption spectroscopy data support this hypothesis, and it explains the observed loss of stereochemistry in the products. In the initial step, either C-C or C-X bond breaking may occur, and the preferred route depends on the substitution pattern of the ring, the type of heteroatom, and various experimental conditions. To better accommodate spin and charge, C-X cleavage happens more frequently, especially in the radical anionic version of the reaction. The addition or withdrawal of a single electron provides a new complementary synthetic strategy to activate hetero-cycloreversions. Despite its potential, this strategy remains largely unexplored. However, it offers a useful method to achieve C=X/olefin metathesis or, upon ring expansion, to construct six-membered heterocyclic rings.Financial support from the Spanish Government (Grants CTQ2010-14882, SEV2012-0267, and JCI-2010-06204) and the Generalitat Valenciana (Prometeo II/2013/005) is gratefully acknowledged.Pérez Ruiz, R.; Jiménez Molero, MC.; Miranda Alonso, MÁ. (2014). Hetero-cycloreversions Mediated by Photoinduced Electron Transfer. Accounts of Chemical Research. 47(4):1359-1368. https://doi.org/10.1021/ar4003224S1359136847

Neutral histidine and photoinduced electron transfer in DNA photolyases

The two major UV−induced DNA lesions, the cyclobutane pyrimidine dimers (CPD) and (6−4) pyrimidine−pyrimidone photoproducts, can be repaired by the light−activated enzymes CPD and (6−4) photolyases, respectively. It is a long−standing question how the two classes of photolyases with alike molecular structure are capable of reversing the two chemically different DNA photoproducts. In both photolyases the repair reaction is initiated by photoinduced electron transfer from the hydroquinone−anion part of the flavin adenine dinucleotide (FADH−) cofactor to the photoproduct. Here, the state−of−the−art XMCQDPT2−CASSCF approach was employed to compute the excitation spectra of the respective active site models. It is found that protonation of His365 in the presence of the hydroquinone−anion electron donor causes spontaneous, as opposed to photoinduced, coupled proton and electron transfer to the (6−4) photoproduct. The resulting neutralized biradical, containing the neutral semiquinone and the N3'−protonated (6−4) photoproduct neutral radical, corresponds to the lowest energy electronic ground−state minimum. The high electron affinity of the N3'−protonated (6−4) photoproduct underlines this finding. Thus, it is anticipated that the (6−4) photoproduct repair is assisted by His365 in its neutral form, which is in contrast to the repair mechanisms proposed in the literature. The repair via hydroxyl group transfer assisted by neutral His365 is considered. The repair involves the 5'base radical anion of the (6−4) photoproduct which in terms of electronic structure is similar to the CPD radical anion. A unified model of the CPD and (6−4) photoproduct repair is propose

Spiers Memorial Lecture. Introductory lecture: the impact of structure on photoinduced processes in nucleic acids and proteins

Light is an important environmental variable and most organisms have evolved means to sense, exploit or avoid it and to repair detrimental effects on their genome. In general, light absorption is the task of specific chromophores, however other biomolecules such as oligonucleotides also do so which can result in undesired outcomes such as mutations and cancer. Given the biological importance of light-induced processes and applications for imaging, optogenetics, photodynamic therapy or photovoltaics, there is a great interest in understanding the detailed molecular mechanisms of photoinduced processes in proteins and nucleic acids. The processes are typically characterized by time-resolved spectroscopic approaches or computation, inferring structural information on transient species from stable ground state structures. Recently, however, structure determination of excited states or other short-lived species has become possible with the advent of X-ray free-electron lasers. This review gives an overview of the impact of structure on the understanding of photoinduced processes in macromolecules, focusing on systems presented at this Faraday Discussion meeting