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111.
Daniel Wechsler Cynthia Carolina Fernndez Julia Kbl Lisa-Marie Augustin Corinna Stumm Norbert Jux Hans-Peter Steinrück Federico Jos Williams Ole Lytken 《Molecules (Basel, Switzerland)》2021,26(10)
Porphyrins are large organic molecules that are interesting for different applications, such as photovoltaic cells, gas sensors, or in catalysis. For many of these applications, the interactions between adsorbed molecules and surfaces play a crucial role. Studies of porphyrins on surfaces typically fall into one of two groups: (1) evaporation onto well-defined single-crystal surfaces under well-controlled ultrahigh vacuum conditions or (2) more application-oriented wet chemical deposition onto less well-defined high surface area surfaces under ambient conditions. In this study, we will investigate the wet chemical deposition of 5-(monocarboxyphenyl)-10,15,20-triphenylporphyrin (MCTPP) on well-defined rutile TiO2(110) single crystals under ambient conditions. Prior to deposition, the TiO2(110) crystals were also cleaned wet-chemically under ambient conditions, meaning none of the preparation steps were done in ultrahigh vacuum. However, after each preparation step, the surfaces were characterized in ultrahigh vacuum with X-ray photoelectron spectroscopy (XPS) and the result was compared with porphyrin layers prepared in ultrahigh vacuum (UHV) by evaporation. The differences of both preparations when exposed to zinc ion solutions will also be discussed. 相似文献
112.
If the baryon asymmetry of the Universe is produced by leptogenesis, CP violation is required in the lepton sector. In the seesaw extension of the standard model with three hierarchical right-handed neutrinos, we show that the baryon asymmetry is insensitive to the Pontecorvo-Maki-Nagakawa-Sakata phases: thermal leptogenesis can work for any value of the observable phases. This result was well known when there were no flavor effects in leptogenesis; we show that it remains true when flavor effects are included. 相似文献
113.
We consider rotationally invariant states in CN1⊗CN2 Hilbert space with even N1?4 and arbitrary N2?N1, and show that in such case there always exist states which are inseparable and remain positive after partial transposition, and thus the PPT criterion does not suffice to prove separability in such systems. We demonstrate it applying a map developed recently by Breuer [H.-P. Breuer, Phys. Rev. Lett. 97 (2006) 080501] to states that remain invariant after partial time reversal. 相似文献
114.
Julia Burrill Rachel Hotta Barbara Daniel Nunzianda Frascione 《Electrophoresis》2021,42(16):1594-1604
Successful forensic DNA profiling from handled items is increasingly routine in casework. This “touch DNA” is thought to contain both cellular and acellular nucleic acid sources. However, there is little clarity on the origins or characteristics of this material. The cellular component consists of anucleate, terminally differentiated corneocytes (assumed to lack DNA), and the occasional nucleated cell. The acellular DNA source is fragmentary, presumably cell breakdown products. This study examines the relative contributions each component makes to the hand-secretions (endogenous) and hand-accumulations (exogenous) by recovering rinses from the inside and outside of worn gloves. Additionally, cellular and acellular DNA was measured at timepoints up to 2 h after hand washing, both with and without interim contact. Microscopic examination confirmed cell morphology and presence of nucleic acids. Following the novel application of a hair keratinocyte lysis method and plasma-DNA fragment purification to hand rinse samples, DNA profiles were generated from both fractions. Exogenous cell-free DNA is shown to be a significant source of touch DNA, which reaccumulates quickly, although its amplifiable nuclear alleles are limited. Endogenous DNA is mostly cellular in origin and provides more allelic information consistently over time. 相似文献
115.
Julia Beerhues Maren Neubrand Dr. Sebastian Sobottka Dr. Nicolás I. Neuman Hannes Aberhan Shubhadeep Chandra Prof. Dr. Biprajit Sarkar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(21):6557-6568
Carbene-based radicals are important for both fundamental and applied chemical research. Herein, extensive electrochemical investigations of nine different 1,2,3-triazolylidene selenium adducts are reported. It is found that the half-wave potentials of the first reduction of the selones correlate with their calculated LUMO levels and the LUMO levels of the corresponding triazolylidene-based mesoionic carbenes (MICs). Furthermore, unexpected quasi-reversibility of the reduction of two triazoline selones, exhibiting comparable reduction potentials, was discovered. Through UV/Vis/NIR and EPR spectroelectrochemical investigations supported by DFT calculations, the radical anion was unambiguously assigned to be triazoline centered. This electrochemical behavior was transferred to a triazolylidene-type MIC-gold phenyl complex resulting in a MIC-radical coordinated AuI species. Apart from UV-Vis-NIR and EPR spectroelectrochemical investigations of the reduction, the reduced gold-coordinated MIC radical complex was also formed in situ in the bulk through chemical reduction. This is the first report of a monodentate triazolylidene-based MIC ligand that can be reduced to its anion radical in a metal complex. The results presented here provide design principles for stabilizing radicals based on MICs. 相似文献
116.
Dr. Goutam Kumar Kole Dr. Julia Merz Dr. Anissa Amar Dr. Bruno Fontaine Dr. Abdou Boucekkine Dr. Jörn Nitsch Sabine Lorenzen Dr. Alexandra Friedrich Dr. Ivo Krummenacher Marta Košćak Prof. Dr. Holger Braunschweig Prof. Dr. Ivo Piantanida Prof. Dr. Jean-François Halet Prof. Dr. Klaus Müller-Buschbaum Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(8):2837-2853
Two N-methylpyridinium compounds and analogous N-protonated salts of 2- and 2,7-substituted 4-pyridyl-pyrene compounds were synthesised and their crystal structures, photophysical properties both in solution and in the solid state, electrochemical and spectroelectrochemical properties were studied. Upon methylation or protonation, the emission maxima are significantly bathochromically shifted compared to the neutral compounds, although the absorption maxima remain almost unchanged. As a result, the cationic compounds show very large apparent Stokes shifts of up to 7200 cm−1. The N-methylpyridinium compounds have a single reduction at ca. −1.5 V vs. Fc/Fc+ in MeCN. While the reduction process was reversible for the 2,7-disubstituted compound, it was irreversible for the mono-substituted one. Experimental findings are complemented by DFT and TD-DFT calculations. Furthermore, the N-methylpyridinium compounds show strong interactions with calf thymus (ct)-DNA, presumably by intercalation, which paves the way for further applications of these multi-functional compounds as potential DNA-bioactive agents. 相似文献
117.
Parajuli Prakash Acharya Sanjit Shamshina Julia L. Abidi Noureddine 《Cellulose (London, England)》2021,28(12):7559-7577
Cellulose - In this study, alkali and alkaline earth metal chlorides with different cationic radii (LiCl, NaCl, and KCl, MgCl2, and CaCl2) were used to gain insight into the behavior of cellulose... 相似文献
118.
Anna Rabe Julia Büker Dr. Soma Salamon Adarsh Koul Dr. Ulrich Hagemann Dr. Joachim Landers Dr. Klaus Friedel Ortega Dr. Baoxiang Peng Prof. Dr. Martin Muhler Prof. Dr. Heiko Wende Prof. Dr. Wolfgang Schuhmann Prof. Dr. Malte Behrens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(68):17038-17048
By using the crystalline precursor decomposition approach and direct co-precipitation the composition and mesostructure of cobalt-based spinels can be controlled. A systematic substitution of cobalt with redox-active iron and redox-inactive magnesium and aluminum in a cobalt spinel with anisotropic particle morphology with a preferred 111 surface termination is presented, resulting in a substitution series including Co3O4, MgCo2O4, Co2FeO4, Co2AlO4 and CoFe2O4. The role of redox pairs in the spinels is investigated in chemical water oxidation by using ceric ammonium nitrate (CAN test), electrochemical oxygen evolution reaction (OER) and H2O2 decomposition. Studying the effect of dominant surface termination, isotropic Co3O4 and CoFe2O4 catalysts with more or less spherical particles are compared to their anisotropic analogues. For CAN-test and OER, Co3+ plays the major role for high activity. In H2O2 decomposition, Co2+ reveals itself to be of major importance. Redox active cations in the structure enhance the catalytic activity in all reactions. A benefit of a predominant 111 surface termination depends on the cobalt oxidation state in the as-prepared catalysts and the investigated reaction. 相似文献
119.
Corrigendum: Combined Two‐Photon Excitation and d→f Energy Transfer in a Water‐Soluble IrIII/EuIII Dyad: Two Luminescence Components from One Molecule for Cellular Imaging
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120.
1,10‐Phenanthroline and Non‐Symmetrical 1,3,5‐Triazine Dipicolinamide‐Based Ligands For Group Actinide Extraction
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Dr. Julia Bisson Dr. Jérémy Dehaudt Dr. Marie‐Christine Charbonnel Dr. Denis Guillaneux Dr. Manuel Miguirditchian Dr. Cécile Marie Nathalie Boubals Guy Dutech Dr. Muriel Pipelier Dr. Virginie Blot Prof. Didier Dubreuil 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7819-7829
The synthesis and evaluation of new extractants for spent nuclear fuel reprocessing are described. New bitopic ligands constituted of phenanthroline and 1,3,5‐triazine cores functionalized by picolinamide groups were designed. Synthetic routes were investigated and optimized to obtain twelve new polyaza‐heterocyclic ligands. In particular, an efficient and versatile methodology was developed to access non‐symmetric 2‐substituted‐4,6‐di(6‐picolin‐2‐yl)‐1,3,5‐triazines from the 1,3,5‐triazapentadiene precursor in the presence of anhydride reagents. Extraction studies showed the ability of both ligand series to extract and separate actinides selectively at different oxidation states (UVI, NpV,VI, AmIII, CmIII, and PuIV) from an acidic solution (3 M HNO3). Phenanthroline‐based ligands show the most promising efficiency for use in the group actinide extraction (GANEX) process due to a higher number of donor nitrogen atoms and a suitable pre‐organization of the dipicolinamide‐1,10‐phenanthroline architecture. 相似文献