Electron-phonon interactions in MoS2ﾠprobed with ultrafast two-dimensional visible/far-infrared spectroscopy

An ultrafast two-dimensional visible/far-IR spectroscopy based on the IR/THz air biased coherent detection method and scanning the excitation frequencies is developed. The method allows the responses in the far-IR region caused by various electronic excitations in molecular or material systems to be observed in real time. Using the technique, the relaxation dynamics of the photo-excited carriers and electron/phonon coupling in bulk MoS2 are investigated. It is found that the photo-generation of excited carriers occurs within two hundred fs and the relaxation of the carriers is tens of ps. The electron-phonon coupling between the excitations of electrons and the phonon mode E1u of MoS2 is also directly observed. The electron excitation shifts the frequency of the phonon mode 9 cm−1 higher, resulting in an absorption peak at 391 cm−1 and a bleaching peak at 382 cm−1. The frequency shift diminishes with the relaxation of the carriers

Dynamics and mechanism of repair of ultraviolet-induced (6–4) photoproduct by photolyase

One of the detrimental effects of UV radiation on DNA is the formation of the (6-4) photoproduct (6-4PP) between two adjacent pyrimidines1. This lesion interferes with replication and transcription and may result in mutation and cell death2. In many organisms a flavoenzyme called photolyase uses blue light energy to repair the 6-4PP3. The molecular mechanism of the repair reaction is poorly understood. Here, we use ultrafast spectroscopy to show that the key step in the repair photocycle is a cyclic proton transfer between the enzyme and the substrate. By femtosecond synchronization of the enzymatic dynamics with the repair function, we followed the function evolution and observed direct electron transfer from the excited flavin cofactor to the 6-4PP in 225 ps but surprisingly fast back electron transfer in 50 ps without repair. Strikingly, we found that the catalytic proton transfer between a histidine residue in the active site and the 6-4PP, induced by the initial photoinduced electron transfer from the excited flavin cofactor to 6-4PP, occurs in 425 ps and leads to 6-4PP repair in tens of nanoseconds. These key dynamics define the repair photocycle and explain the underlying molecular mechanism of the enzyme’s modest efficiency

The molecular origin of high DNA-repair efficiency by photolyase

The primary dynamics in photomachinery such as charge separation in photosynthesis and bond isomerization in sensory photoreceptor are typically ultrafast to accelerate functional dynamics and avoid energy dissipation. The same is also true for the DNA repair enzyme, photolyase. However, it is not known how the photoinduced step is optimized in photolyase to attain maximum efficiency. Here, we analyse the primary reaction steps of repair of ultraviolet-damaged DNA by photolyase using femtosecond spectroscopy. With systematic mutations of the amino acids involved in binding of the flavin cofactor and the cyclobutane pyrimidine dimer substrate, we report our direct deconvolution of the catalytic dynamics with three electron-transfer and two bond-breaking elementary steps and thus the fine tuning of the biological repair function for optimal efficiency. We found that the maximum repair efficiency is not enhanced by the ultrafast photoinduced process but achieved by the synergistic optimization of all steps in the complex repair reaction

Electron Tunneling Pathways and Role of Adenine in Repair of Cyclobutane Pyrimidine Dimer by DNA Photolyase

Electron tunneling pathways in enzymes are critical to their catalytic efficiency. Through electron tunneling, photolyase, a photoenzyme, splits UV-induced cyclobutane pyrimidine dimer into two normal bases. Here, we report our systematic characterization and analyses of photo-initiated three electron transfer processes and cyclobutane ring splitting by following the entire dynamical evolution during enzymatic repair with femtosecond resolution. We observed the complete dynamics of the reactants, all intermediates and final products, and determined their reaction time scales. Using (deoxy)uracil and thymine as dimer substrates, we unambiguously determined the electron tunneling pathways for the forward electron transfer to initiate repair and for the final electron return to restore the active cofactor and complete the catalytic photocycle. Significantly, we found that the adenine moiety of the unusual bent flavin cofactor is essential to mediating all electron-transfer dynamics through a super-exchange mechanism, leading to a delicate balance of time scales. The cyclobutane ring splitting takes tens of picoseconds while electron-transfer dynamics all occur on a longer time scale. The active-site structural integrity, unique electron tunneling pathways and the critical role of adenine assure the synergy of these elementary steps in this complex photorepair machinery to achieve maximum repair efficiency which is close to unity. Finally, we used the Marcus electron-transfer theory to evaluate all three electron transfer processes and thus obtained their reaction driving forces (free energies), reorganization energies, and electronic coupling constants, concluding the forward and futile back electron transfer in the normal region and that the final electron return of the catalytic cycle is in the inverted region

Energy consumption and GHG emissions of six biofuel pathways by LCA in (the) People's Republic of China

This paper presents life-cycle-analysis (LCA) energy consumption (EC) and greenhouse gas (GHG) emissions of China's current six biofuel pathways, which are: corn-derived ethanol (CE); cassava-derived ethanol (KE); sweet sorghum-derived ethanol (SE); soybean-derived bio-diesel (SB); jatropha fruit-derived bio-diesel (JB); and used cooking oil (UCO)-derived bio-diesel (UB). The tool utilized here is the WTW (Well-to-Wheels) module of Tsinghua-CA3EM model covering the entire lifecycle including: raw materials cultivation (or feedstock collection); fuel production; transportation and distribution; and application in automobile engines, compared with Conventional Petroleum-based gasoline and diesel Pathways (CPP). The results indicate: (1) the fossil energy inputs are about 1.0-1.5 times the energy contained in the fuel for the CE, SE and SB pathways, but 0.5-0.9 times for the KE, UB and JB pathways; (2) compared with CPP, the JB, KE and UB pathways can reduce both fossil fuel consumption and GHG emissions; the CE and SB pathways can only reduce fossil fuel consumption, but increase GHG emission; the SE pathway increases not only fossil fuel consumption but also GHG emission; and (3) the main factors inducing high EC and GHG emission levels include: high EC levels during the fuel production stage and high fertilizer application rates during the planting of raw feedstocks. Conclusions are that of the aforementioned biofuel pathways in (the) People's Republic of China: (1) only the JB, KE and UB pathways have energy-saving merits as indicated by the LCA energy inputs and outputs; (2) compared with CPP, all but the SE pathway reduces fossil fuel consumption. However, the SB and CE pathway increase GHG emission; (3) all six displace petroleum by utilizing more coal; and (4) feedstock productivity levels must be increased, and there must be a reduction in fertilizer utilization and EC consumption during the cultivation and transportation stages in order to achieve the goals of energy balance and GHG emission reduction.(the) People' s Republic of China Greenhouse gas Energy consumption Biofuel Bio-ethanol Bio-diesel

rapidinternalconversioninasymmetricmoleculeld700studiedbymeansoffemtosecondfluorescencedepletion

The rapid internal conversion dynamics at room temperature is determined by using the femtosecond time-resolved fluorescence depletion measurements of a complex solvated molecule of LD700 (rhodamine 700) combined with steady-state absorption and fluorescence spectroscopy, as well as quantum chemical calculation. The molecule is excited by a 50 fs laser pulse at 400 nm which directly populated the highly excited singlet state, the rapid internal conversions (ICs) are observed, which leads to the directional changes of the emission transition moment following photoexcitation to the highly excited singlet state S-5 of LD 700