抗原变异可使得多种致病微生物易于逃避宿主免疫应答。表达在感染红细胞表面的恶性疟原虫红细胞表面蛋白1（PfPMP1）与感染红细胞、内皮细胞、树突状细胞以及胎盘的单个或多个受体作用，在黏附及免疫逃避中起关键的作用。每个单倍体基因组var基因家族编码约60种成员，通过启动转录不同的var基因变异体为抗原变异提供了分子基础。

疟原虫var基因转换速率变化导致抗原变异[英]／Paul H, Robert P, Christodoulou Z, et al//Proc Natl Acad Sci U S A

Catalysts for chemical and electrochemical reactions underpin many aspects of modern technology and industry, from energy storage and conversion to toxic emissions abatement to chemical and materials synthesis. This role necessitates the design of highly active, stable, yet earth-abundant heterogeneous catalysts. In this Review, we present the perovskite oxide family as a basis for developing such catalysts for (electro)chemical conversions spanning carbon, nitrogen, and oxygen chemistries. A framework for rationalizing activity trends and guiding perovskite oxide catalyst design is described, followed by illustrations of how a robust understanding of perovskite electronic structure provides fundamental insights into activity, stability, and mechanism in oxygen electrocatalysis. We conclude by outlining how these insights open experimental and computational opportunities to expand the compositional and chemical reaction space for next-generation perovskite catalysts.

http://science.sciencemag.org/content/sci/358/6364/751.full.pdf

Perovskites in catalysis and electrocatalysis

This self-contained, comprehensive book describes the fundamental properties of soft x-rays and extreme ultraviolet (EUV) radiation and discusses their applications in a wide variety of fields, including EUV lithography for semiconductor chip manufacture and soft x-ray biomicroscopy. The author begins by presenting the relevant basic principles such as radiation and scattering, wave propagation, diffraction, and coherence. He then goes on to examine a broad range of phenomena and applications. The topics covered include EUV lithography, biomicroscopy, spectromicroscopy, EUV astronomy, synchrotron radiation, and soft x-ray lasers. He also provides a great deal of useful reference material such as electron binding energies, characteristic emission lines and photo-absorption cross-sections. The book will be of great interest to graduate students and researchers in engineering, physics, chemistry, and the life sciences. It will also appeal to practicing engineers involved in semiconductor fabrication and materials science.

X-Rays and Extreme Ultraviolet Radiation: Principles and Applications

When intense light interacts with an atomic gas, recollision between an ionizing electron and its parent ion creates high-order harmonics of the fundamental laser frequency. This sub-cycle effect generates coherent soft X-rays and attosecond pulses, and provides a means to image molecular orbitals. Recently, high harmonics have been generated from bulk crystals, but what mechanism dominates the emission remains uncertain. To resolve this issue, we adapt measurement methods from gas-phase research to solid zinc oxide driven by mid-infrared laser fields of 0.25 volts per angstrom. We find that when we alter the generation process with a second-harmonic beam, the modified harmonic spectrum bears the signature of a generalized recollision between an electron and its associated hole. In addition, we find that solid-state high harmonics are perturbed by fields so weak that they are present in conventional electronic circuits, thus opening a route to integrate electronics with attosecond and high-harmonic technology. Future experiments will permit the band structure of a solid to be tomographically reconstructed.

/pdf/linking-high-harmonics-from-gases-and-solids-4rtfjbqvr5.pdf

Linking high harmonics from gases and solids

Acceleration and collision of particles has been a key strategy for exploring the texture of matter. Strong light waves can control and recollide electronic wavepackets, generating high-harmonic radiation that encodes the structure and dynamics of atoms and molecules and lays the foundations of attosecond science. The recent discovery of high-harmonic generation in bulk solids combines the idea of ultrafast acceleration with complex condensed matter systems, and provides hope for compact solid-state attosecond sources and electronics at optical frequencies. Yet the underlying quantum motion has not so far been observable in real time. Here we study high-harmonic generation in a bulk solid directly in the time domain, and reveal a new kind of strong-field excitation in the crystal. Unlike established atomic sources, our solid emits high-harmonic radiation as a sequence of subcycle bursts that coincide temporally with the field crests of one polarity of the driving terahertz waveform. We show that these features are characteristic of a non-perturbative quantum interference process that involves electrons from multiple valence bands. These results identify key mechanisms for future solid-state attosecond sources and next-generation light-wave electronics. The new quantum interference process justifies the hope for all-optical band-structure reconstruction and lays the foundation for possible quantum logic operations at optical clock rates.

Real-time observation of interfering crystal electrons in high-harmonic generation

It is well known that ultraviolet photoexcitation of iron pentacarbonyl results in rapid loss of carbonyl ligands leading to the formation of coordinatively unsaturated iron carbonyl compounds. We employ ultrafast mid-infrared transient absorption spectroscopy to probe the photodissociation dynamics of gas-phase iron pentacarbonyl following ultraviolet excitation at 265 and 199 nm. After photoexcitation at 265 nm, our results show evidence for sequential dissociation of iron pentacarbonyl to form iron tricarbonyl via a short-lived iron tetracarbonyl intermediate. Photodissociation at 199 nm results in the prompt production of Fe(CO)3 within 0.25 ps via several energetically accessible pathways. An additional 15 ps time constant extracted from the data is tentatively assigned to intersystem crossing to the triplet manifold of iron tricarbonyl or iron dicarbonyl. Mechanisms for formation of iron tetracarbonyl, iron tricarbonyl, and iron dicarbonyl are proposed and theoretically validated with one-dimensional cuts through the potential energy surface as well as bond dissociation energies. Ground state calculations are computed at the CCSD(T) level of theory and excited states are computed with EOM-EE-CCSD(dT).

Ultraviolet photodissociation of gas-phase iron pentacarbonyl probed with ultrafast infrared spectroscopy.

Shock-induced detonation is a key property of energetic materials (EM) that remains empirically understood. One proposed mechanism of shock-initiation in EM is “phonon up-pumping” to initiate chemical reactions, where excitation of lattice phonon modes rapidly transfers energy into intramolecular vibrations, ultimately resulting in the breaking of chemical bonds. We are developing novel ultrafast laser spectroscopy techniques to study vibrational energy transfer from phonon modes to intramolecular vibrations (phonon up-pumping), as well as competing energy transfer pathways from intramolecular vibrations to phonon modes (vibrational cooling). Through combinations of plasma- generated supercontinuum infrared, tunable near- and mid-infrared, and terahertz pulses in pump-probe spectroscopy, supplemented with ab inito simulations, we can explore the energy transfer processes on a sub-picosecond time scale to elucidate vibrational energy transfer pathways and lifetimes in EM. Herein we highlight recent progress, including the spectral and temporal characteristics of the infrared and THz sources as well as preliminary results on select EM.

Ultrafast spectroscopic studies of vibrational energy transfer in energetic materials

We investigated the reaction of O(3P) with cyclopentene at 4 Torr and 298 K using time-resolved multiplexed photoionization mass spectrometry, where O(3P) radicals were generated by 351 nm photolysis of NO2 and reacted with excess cyclopentene in He under pseudo-first-order conditions. The resulting products were sampled, ionized, and detected by tunable synchrotron vacuum ultraviolet radiation and an orthogonal acceleration time-of-flight mass spectrometer. This technique enabled measurement of both mass spectra and photoionization spectra as functions of time following the initiation of the reaction. We observe propylketene (41%), acrolein + ethene (37%), 1-butene + CO (19%), and cyclopentene oxide (3%), of which the propylketene pathway was previously unidentified experimentally and theoretically. The automatically explored reactive potential energy landscape at the CCSD(T)-F12a/cc-pVTZ//ωB97X-D/6-311++G(d,p) level and the related master equation calculations predict that cyclopentene oxide is formed on the singlet potential energy surface, whereas propylketene is first formed on the triplet surface. These calculations provide evidence that significant intersystem crossing can happen in this reaction not only around the geometry of the initial triplet adduct but also around that of triplet propylketene. The formation of 1-butene + CO is initiated on the triplet surface, with bond cleavage and hydrogen transfer occurring during intersystem crossing to the singlet surface. At present, we are unable to explain the mechanistic origins of the acrolein + ethene channel, and we thus refrain from assigning singlet or triplet reactivity to this channel. Overall, at least 60% of the products result from triplet reactivity. We propose that the reactivity of cyclic alkenes with O(3P) is influenced by their greater effective degree of unsaturation compared with acyclic alkenes. This work also suggests that searches for minimum-energy crossing points that connect triplet surfaces to singlet surfaces should extend beyond the initial adducts.

Krupa Ramasesha

Papers

Ultraviolet photodissociation of gas-phase iron pentacarbonyl probed with ultrafast infrared spectroscopy.

Ultrafast spectroscopic studies of vibrational energy transfer in energetic materials

A New Pathway for Intersystem Crossing: Unexpected Products in the O(3P) + Cyclopentene Reaction.

Collective vibrations of water-solvated hydroxide ions investigated with broadband 2dir spectroscopy

Experimental and Theoretical Studies of Ultrafast Vibrational Energy Transfer Dynamics in Energetic Materials.