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81.
Szymon Godlewski Jakub S. Prauzner-Bechcicki Janusz Budzioch Lukasz Walczak Irena G. Stará Ivo Starý Petr Sehnal Marek Szymonski 《Surface science》2012,606(21-22):1600-1607
Helicenes are carbon-rich materials with an ordered structure that possess interesting and remarkable electronic, chiroptical, mechanical and magnetic properties either in bulk or as single molecule devices. We report on the first attempt to anchor and organize [11]anthrahelicene ([11]AH) molecules onto a metal oxide surface. Molecular structures obtained on the (110) and (011) faces of rutile titania are characterized using scanning probe microscopy. On the (110) surface, [11]AH molecules form islands that are comprised of small domains of two types that are mirror reflections of each other and have an ordered quasi-hexagonal lattice. In contrast, molecules form unordered clusters on the (011) surface. Single molecules on both faces are imaged with sub-molecular resolution. 相似文献
82.
Dr. Rubén D. Costa Dr. Juan Aragó Prof. Dr. Enrique Ortí Dr. Ted M. Pappenfus Prof. Dr. Kent R. Mann Dr. Katarzyna Matczyszyn Prof. Dr. Marek Samoc Dr. José L. Zafra Prof. Dr. Juan T. López Navarrete Prof. Dr. Juan Casado 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1476-1488
The linear and non‐linear optical properties of a family of dumbbell‐shaped dinuclear complexes, in which an oligothiophene chain with various numbers of rings (1, 3, and 6) acts as a bridge between two homoleptic tris(2,2′‐bipyridine)ruthenium(II) complexes, have been fully investigated by using a range of spectroscopic techniques (absorption and luminescence, transient absorption, Raman, and non‐linear absorption), together with density functional theory calculations. Our results shed light on the impact of the synergistic collaboration between the electronic structures of the two chemical moieties on the optical properties of these materials. Experiments on the linear optical properties of these compounds indicated that the length of the oligothiophene bridge was critical for luminescent behavior. Indeed, no emission was detected for compounds with long oligothiophene bridges (compounds 3 and 4 , with 3 and 6 thiophene rings, respectively), owing to the presence of the 3π? π* state of the conjugated bridge below the 3MLCT‐emitting states of the end‐capping RuII complexes. In contrast, the compound with the shortest bridge ( 2 , one thiophene ring) shows excellent photophysical features. Non‐linear optical experiments showed that the investigated compounds were strong non‐linear absorbers in wide energy ranges. Indeed, their non‐linear absorption was augmented upon increasing the length of the oligothiophene bridge. In particular, the compound with the longest oligothiophene bridge not only showed strong two‐photon absorption (TPA) but also noteworthy three‐photon‐absorption behavior, with a cross‐section value of 4×10?78 cm6 s2 at 1450 nm. This characteristic was complemented by the strong excited‐state absorption (ESA) that was observed for compounds 3 and 4 . As a matter of fact, the overlap between the non‐linear absorption and ESA establishes compounds 3 and 4 as good candidates for optical‐power‐limiting applications. 相似文献
83.
Dr. Benjamin J. Coe Dr. Simon P. Foxon Dr. Madeleine Helliwell Dr. Daniela Rusanova Dr. Bruce S. Brunschwig Prof. Dr. Koen Clays Griet Depotter Dr. Marcin Nyk Prof. Dr. Marek Samoc Dominika Wawrzynczyk Prof. Dr. Javier Garín Dr. Jesús Orduna 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(21):6613-6629
New complexes with six ferrocenyl (Fc) groups connected to ZnII or CdII tris(2,2′‐bipyridyl) cores are described. A thorough characterisation of their BPh4? salts includes two single‐crystal X‐ray structures, highly unusual for such species with multiple, extended substituents. Intense, visible d(FeII)→π* metal‐to‐ligand charge‐transfer (MLCT) bands accompany the π→π* intraligand charge‐transfer absorptions in the near UV region. Each complex shows a single, fully reversible FeIII/II wave when probed electrochemically. Molecular quadratic nonlinear optical (NLO) responses are determined by using hyper‐Rayleigh scattering and Stark spectroscopy. The latter gives static first hyperpolarisabilities β0 reaching as high as approximately 10?27 esu and generally increasing with π‐conjugation extension. Z‐scan cubic NLO measurements reveal high two‐photon absorption cross‐sections σ2 of up to 5400 GM in one case. DFT calculations reproduce the π‐conjugation dependence of β0, and TD‐DFT predicts three transitions close in energy contributing to the MLCT bands. The lowest energy transition has octupolar character, whereas the other two are degenerate and dipolar in nature. 相似文献
84.
Danielly S. Campos-Ferreira Gustavo A. Nascimento Elaine V.M. Souza Maria A. Souto-Maior Mariana S. Arruda Deborah M.L. Zanforlin Marek H.F. Ekert Danyelly Bruneska José L. Lima-Filho 《Analytica chimica acta》2013
An electrochemical DNA biosensor for human papillomavirus (HPV) 16 detection has been developed. For this proposed biosensor, l-cysteine was first electrodeposited on the gold electrode surface to form l-cysteine film (CYSFILM). Subsequently, HPV16-specific probe was immobilized on the electrode surface with CYSFILM. Electrochemistry measurement was studied by differential pulse voltammetry method (DPV). The measurement was based on the reduction signals of methylene blue (MB) before and after hybridization either between probe and synthetic target or extracted DNA from clinical samples. The effect of probe concentration was analyzed and the best results were seen at 1000 nM. The hybridization detection presented high sensitivity and broad linear response to the synthetic-target concentration comprised between 18.75 nM and 250 nM as well as to a detection limit of 18.13 nM. The performance of this biosensor was also investigated by checking probe-modified electrode hybridization with extracted DNA from samples. The results showed that the biosensor was successfully developed and exhibited high sensitivity and satisfactory selectivity to HPV16. These results allow for the possibility of developing a new portable detection system for HPVs and for providing help in making an effective diagnosis in the early stages of infection. 相似文献
85.
Subsequent treatment of N-crotoyl-(1S,2R)-bornane-10,2-sultam with EtMgCl, recrystallization of the product and saponification, afforded R-(-)-3-methylpenthanoic acid which was used for acylation of (1R,2S)-bornane-10,2-sultam. The product was converted into N-[(2S,3R)-2-amino-3-methylpentanoyl]-(1R,2S)-bornane-10,2-sultam by hydroxyamination with 1-chloro-1-nitrosocyclohexane, followed by reduction of the hydroxylamine grouping. Saponification of the sultam imide provided (+)-alloisoleucine. 相似文献
86.
Stanislav Standara Petr Kulhánek Radek Marek Michal Straka 《Journal of computational chemistry》2013,34(22):1890-1898
The isotropic 129Xe nuclear magnetic resonance (NMR) chemical shift (CS) in Xe@C60 dissolved in liquid benzene was calculated by piecewise approximation to faithfully simulate the experimental conditions and to evaluate the role of different physical factors influencing the 129Xe NMR CS. The 129Xe shielding constant was obtained by averaging the 129Xe nuclear magnetic shieldings calculated for snapshots obtained from the molecular dynamics trajectory of the Xe@C60 system embedded in a periodic box of benzene molecules. Relativistic corrections were added at the Breit–Pauli perturbation theory (BPPT) level, included the solvent, and were dynamically averaged. It is demonstrated that the contribution of internal dynamics of the Xe@C60 system represents about 8% of the total nonrelativistic NMR CS, whereas the effects of dynamical solvent add another 8%. The dynamically averaged relativistic effects contribute by 9% to the total calculated 129Xe NMR CS. The final theoretical value of 172.7 ppm corresponds well to the experimental 129Xe CS of 179.2 ppm and lies within the estimated errors of the model. The presented computational protocol serves as a prototype for calculations of 129Xe NMR parameters in different Xe atom guest–host systems. © 2013 Wiley Periodicals, Inc. 相似文献
87.
Irma Panfil CzesLaw Belzecki Marek Chmielewski 《Journal of carbohydrate chemistry》2013,32(3):463-470
Abstract Saturated lactone 8, easily available by 1,3-dipolar cycloaddition of nitrone 4 to unsaturated lactone 7 was transformed into the β-lactam 22having a polyol side chain at the C-3 position of the azetidinone ring. The same sequence of reactions, when applied to 9 and 10 failed to give the respective β-lactams owing to the removal of the nitrogen atoms from those molecules. 相似文献
88.
Effect of viscosity of a liquid membrane containing oleyl alcohol on the pertraction of butyric acid
Marek Blahušiak Ján Marták Fernando Miranda Štefan Schlosser José A. Teixeira 《Chemical Papers》2013,67(12):1560-1568
Solvent formulation is important in the optimization of the mass-transfer through supported liquid membranes (SLM) in pertraction and membrane extraction. Oleyl alcohol (OA) is frequently used as the solvent or diluent in the extraction of carboxylic acids. A disadvantage of OA is its relatively high viscosity of 28.32 mPa s at 25°C. This can be decreased by the application of a less viscous OA diluent, e.g. dodecane. The relationship between the ratio of the distribution coefficient of butyric acid (BA), D F, and the viscosity of OA-dodecane solvents, µ, as extraction and transport characteristics, and the overall mass-transfer coefficient, K p, through SLMs was analyzed. Dependence of the D F/µ ratio on the OA concentration showed a maximum at the OA concentration of 15 mass % to 30 mass %. The OA concentration dependence of K p for SLMs exhibited also a maximum at about 30 mass % and 20 mass % of OA at the BA concentration driving force of 0.12 kmol m?3 and 0.3 kmol m?3, respectively. Shifting of the maximum in K p dependences towards lower OA concentrations by increasing the BA concentration driving force is in agreement with the D F/µ ratio dependence. Using pure OA as the solvent or diluent is not preferable and a mixture of a low viscosity diluent with the OA concentration below 40 mass % should be used. The presented results show the potential of the D F/µ ratio in the screening and formulation of solvents in extraction and SLM optimization. 相似文献
89.
Marek Gryta 《Chemical Papers》2013,67(9):1201-1209
The separation of diluted ethanol solutions and fermentation broths by membrane distillation was investigated. The influence of stream flow-rate on the ethanol flux was studied. An evaluation of the process conditions on the separation degree of ethanol was performed with the application of hydrophobic capillary membranes composed of polypropylene. By removing the alcohol via membrane distillation, it is possible to achieve a higher content of ethanol in the permeate than that in the broth. The enrichment coefficient amounted to 4–6.5, and decreased with an increase of the ethanol concentration in the broth. It was found that the flow-rate affects the value of the enrichment coefficient. A positive influence of carbon dioxide on the ethanol transport through the capillary membrane was observed. The evolution of CO2 bubbles from the broth increases the stream turbulence, probably enhancing the alcohol concentration in the layer adjacent to the membrane surface. 相似文献
90.