The Excited‐State Dynamics of Phycocyanobilin in Dependence on the Excitation Wavelength

The primary light‐induced processes of phycocyanobilin were studied by means of transient‐grating spectroscopy, whereby the excitation wavelength was varied over the spectral region of the ground‐state absorption. On the basis of the results obtained, both the rate of the photoreaction in phycocyanobilin and the ratio of the decay of different excited‐state species via two decay channels depend on the excitation wavelength. Furthermore, the formation of the photoreaction product is also dependent on the pump color. These data support a recently established model for the primary photoprocesses in phycocyanobilin. In addition, phycocyanobilin protonated at the basic pyrrolenine‐type nitrogen atom was included in the transient absorption study. The decay behavior was found to be almost unchanged when compared with the unprotonated form, and this suggests that protonation of the tetrapyrrole ring structure has no effect on the overall photochemistry.     

Ultrafast dynamics of myoglobin probed by time-resolved resonance Raman spectroscopy

Recent experimental work carried out in this laboratory on the ultrafast dynamics of myoglobin (Mb) is summarized with a stress on structural and vibrational energy relaxation. Studies on the structural relaxation of Mb following CO photolysis revealed that the structural change of heme itself, caused by CO photodissociation, is completed within the instrumental response time of the time-resolved resonance Raman apparatus used (approximately 2 ps). In contrast, changes in the intensity and frequency of the iron-histidine (Fe-His) stretching mode upon dissociation of the trans ligand were found to occur in the picosecond regime. The Fe-His band is absent for the CO-bound form, and its appearance upon photodissociation was not instantaneous, in contrast with that observed in the vibrational modes of heme, suggesting appreciable time evolution of the Fe displacement from the heme plane. The band position of the Fe-His stretching mode changed with a time constant of about 100 ps, indicating that tertiary structural changes of the protein occurred in a 100-ps range. Temporal changes of the anti-Stokes Raman intensity of the v4 and v7 bands demonstrated immediate generation of vibrationally excited heme upon the photodissociation and decay of the excited populations, whose time constants were 1.1 +/- 0.6 and 1.9 +/- 0.6 ps, respectively. In addition, the development of the time-resolved resonance Raman apparatus and prospects in this research field are described.     

Combined IR and XPS analysis of the native (1 0 0) surface of single‐crystalline silicon after HFaq etching

A combined analysis, based on angle‐resolved X‐ray photoelectron spectroscopy and multiple‐internal‐reflection infrared spectroscopy, of the (1 0 0) silicon surface after etching in dilute aqueous solution of HF is presented. The analysis shows that the surface is mainly formed by a heterogeneous distribution of SiH, SiH₂ and SiH₃ terminations, but contains (in addition to sub‐stoichiometric oxidized silicon) a form of reduced silicon, not consistent with the currently accepted picture of the native HF_aq‐etched surface. Copyright © 2007 John Wiley & Sons, Ltd.     

Redox and Conformational Equilibria and Dynamics of Cytochrome c at High Electric Fields

Cytochrome c (Cyt‐c) adsorbed in the electrical double layer of the Ag electrode/electrolyte interface has been studied by stationary and time‐resolved surface‐enhanced resonance Raman spectroscopy to analyse the effect of strong electric fields on structure and reaction equilibria and dynamics of the protein. In the potential range between +0.1 and ?0.55 V (versus saturated calomel electrode), the adsorbed Cyt‐c forms a potential‐dependent reversible equilibrium between the native state B1 and a conformational state B2. The redox potentials of the bis‐histidine‐coordinated six‐coordinated low‐spin and five‐coordinated high‐spin substates of B2 were determined to be ?0.425 and ?0.385 V, respectively, whereas the additional six‐coordinated aquo‐histidine‐coordinated high‐spin substate was found to be redox‐inactive. The redox potential for the conformational state B1 was found to be the same as in solution in agreement with the structural identity of the adsorbed B1 and the native Cyt‐c. For all three redox‐active species, the formal heterogeneous electron transfer rate constants are small and of the same order of magnitude (3–13 s^?1), which implies that the rate‐limiting step is largely independent of the redox‐site structure. These findings, as well as the slow and potential‐dependent transitions between the various conformational (sub‐)states, can be rationalized in terms of an electric field‐induced increase of the activation energy for proton‐transfer steps linked to protein structural reorganisation. Further increasing the electric field strength by shifting the electrode potential above +0.1 V leads to irreversible structural changes that are attributed to an unfolding of the polypeptide chain.     

Time‐resolved in situ tomography for the analysis of evolving metal‐foam granulates

An experimental setup has been developed that allows for capturing up to 25 tomograms s^?1 using the white X‐ray beam at the experimental station EDDI of BESSY II, Berlin, Germany. The key points are the use of a newly developed, precise and fast rotation stage, a very efficient scintillator and a fast CMOS camera. As a first application, the foaming of aluminium alloy granules at 923 K was investigated in situ. Formation and growth of bubbles in the liquid material were observed and found to be influenced by the limited thermal conductivity in the bulk granules. Changes that took place between two tomographic frames separated in time by 39 ms could be detected and analysed quantitatively.     

Studies of Space and Time Resolved Emission Measurements of an ArF Excimer Laser Ablated Plasma

Abstract

A laser ablated plasma created by an ArF excimer laser of wavelength of 193 nm, laser power of 150-200 mJ, repetition rate of 1 Hz, and zinc, copper, iron and nickel targets was studied. Quantitative emission studies are reported that are both space and time resolved. The space results of the laser ablated plasma suggest a confined plasma with a gaussian type distribution of atoms and ions. The time resolved studies show a maximum emission signal occurring at approximately 20 μs with a lifetime of less than 100 μs.     

Chitosan/Ce(IV) redox polymerization‐based amplification for detection of DNA point mutation

Polymerization‐based signal amplification, a technique developed for use in rapid diagnostic tests, hinges on the ability to localize initiators as a function of interfacial binding events. We report here a new DNA detection method in which polymer growth in redox‐polymerization is used as a means to amplify detection signals. The introduction of biotin‐labeled chitosan (biotin‐CS) with highly dense amino groups into the polymerization amplification as macromolecular reducing agent, beneficially simplifies amplification operation, as well as, provides a large amount of initiation points to improve the sensitivity of detection. DNA hybridization, SA and biotin binding reactions led to the attachment of CS on a solid surface where specific DNA sequences were located. With the addition of the mixture containing monomer AM, crosslinker PEGDA and oxidant CAN onto the CS location, the growth of polymer films was triggered to render the corresponding spots readily distinguishable to the naked eye. Direct visualization of 0.21 fmol target DNA molecules of interest was demonstrated. Non‐small cell lung cancer p53 sequence was further selected as a proof‐of‐principle to detect DNA point mutation. The proposed method exhibited an efficient amplification performance for molecule detection, and paved a new way for visual diagnosis of biomolecules. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1929–1937     

Competing energy scales in high‐temperature superconductors: Ultrafast pump–probe studies

We present a review of photoexcited quasiparticle dynamics of cuprate and pnictide high‐temperature superconductors in regimes (temperature, doping) where different phases such as superconductivity, spin‐density‐wave (SDW) and pseudogap phases coexist or compete with one another. We start with the overdoped cuprate superconductor Y_1–xCa_x Ba₂Cu₃O_7–δ, where the superconducting gap and pseudogap coexist in the superconducting state. In another cuprate Tl₂Ba₂Ca₂Cu₃O_y, we ob‐ serve a competition between SDW and superconducting orders deep in the superconducting state. Finally, in the underdoped iron pnictide superconductor (Ba,K)Fe₂As₂, SDW order forms at 85 K, followed by superconductivity at 28 K. We also find the emergence of a normal‐state order that suppresses SDW at a temperature T * ～ 60 K and argue that this normal‐state order is a precursor to superconductivity. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Strategies for differentiation of isobaric flavonoids using liquid chromatography coupled to electrospray ionization mass spectrometry

Flavonoids are a class of secondary plant metabolites existing in great variety in nature. Due to this variety, identification can be difficult, especially as overlapping compounds in both chromatographic separations and mass spectrometric detection are common. Methods for distinguishing isobaric flavonoids using MS² and MS³ have been developed. Chromatographic separation of various plant extracts was done with RP‐HPLC and detected with positive ESI‐MS operated in information‐dependent acquisition (IDA) mode. Two methods for the determination of flavonoid identity and substitution pattern, both featuring IDA criteria, were used together with the HPLC equipment. A third method where the collision energy was ramped utilized direct infusion. With the developed strategies, it is possible to differentiate between many isobaric flavonoids. Various classes of flavonoids were found in all of the plant extracts, in the red onion extract 45 components were detected and for 29 of them the aglycone was characterized, while the substituents were tentatively identified for 31 of them. For the strawberry extract, those numbers were 66, 30 and 60, and for the cherry extract 99, 56 and 71. The great variety of flavonoids, several of them isobaric, found in each of the extracts highlights the need for reliable methods for flavonoid characterization. Methods capable of differentiating between most of the isobars analyzed have been developed. Copyright © 2014 John Wiley & Sons, Ltd.