164 results
Search Results
Now showing 1 - 10 of 164
- ItemDirect synthesis of benzylic amines by palladium-catalyzed carbonylative aminohomologation of aryl halides([London] : Macmillan Publishers Limited, part of Springer Nature, 2018) Peng, Jin-Bao; Wu, Fu-Peng; Xu, Cong; Qi, Xinxin; Ying, Jun; Wu, Xiao-FengBenzylic amines are valuable compounds with important applications in areas including pharmaceuticals and agrochemicals. The known procedures for their synthesis are limited by difficulties in functionalizing the parent aminomethyl groups. On the other hand, carbonylation reactions offer a potent method to introduce carbonyl groups and homologate carbon chains. However, carbonylative aminohomologation of aryl halides is challenging due to competing reactions and the need to balance multiple sequential steps. Here we report a palladium-catalyzed carbonylative aminohomologation reaction for the direct aminomethylation of aryl halides. The reaction proceeds via a tandem palladium-catalyzed formylation, followed by imine formation and formic acid-mediated reduction. Useful functional groups including chloride, bromide, ester, ketone, nitro, and cyano are compatible with this reaction. Both aryl iodides and bromides are suitable substrates and a wide range of synthetically useful amines are efficiently obtained in moderate to excellent yields.
- ItemEfficient alkane oxidation under combustion engine and atmospheric conditions([London] : Macmillan Publishers Limited, part of Springer Nature, 2021) Wang, Zhandong; Ehn, Mikael; Rissanen, Matti P.; Garmash, Olga; Quéléver, Lauriane; Xing, Lili; Monge-Palacios, Manuel; Rantala, Pekka; Donahue, Neil M.; Berndt, Torsten; Sarathy, S. ManiOxidation chemistry controls both combustion processes and the atmospheric transformation of volatile emissions. In combustion engines, radical species undergo isomerization reactions that allow fast addition of O2. This chain reaction, termed autoxidation, is enabled by high engine temperatures, but has recently been also identified as an important source for highly oxygenated species in the atmosphere, forming organic aerosol. Conventional knowledge suggests that atmospheric autoxidation requires suitable structural features, like double bonds or oxygen-containing moieties, in the precursors. With neither of these functionalities, alkanes, the primary fuel type in combustion engines and an important class of urban trace gases, are thought to have minor susceptibility to extensive autoxidation. Here, utilizing state-of-the-art mass spectrometry, measuring both radicals and oxidation products, we show that alkanes undergo autoxidation much more efficiently than previously thought, both under atmospheric and combustion conditions. Even at high concentrations of NOX, which typically rapidly terminates autoxidation in urban areas, the studied C6–C10 alkanes produce considerable amounts of highly oxygenated products that can contribute to urban organic aerosol. The results of this inter-disciplinary effort provide crucial information on oxidation processes in both combustion engines and the atmosphere, with direct implications for engine efficiency and urban air quality.
- ItemElectrochemical growth mechanism of nanoporous platinum layers([London] : Macmillan Publishers Limited, part of Springer Nature, 2021) Stanca, Sarmiza-Elena; Vogt, Oliver; Zieger, Gabriel; Ihring, Andreas; Dellith, Jan; Undisz, Andreas; Rettenmayr, Markus; Schmidt, HeidemariePorous platinum is a frequently used catalyst material in electrosynthesis and a robust broadband absorber in thermoelectrics. Pore size distribution and localization determine its properties by a large extent. However, the pore formation mechanism during the growth of the material remains unclear. In this work we elucidate the mechanism underlying electrochemical growth of nanoporous platinum layers and its control by ionic concentration and current density during electrolysis. The electrode kinetics and reduction steps of PtCl4 on platinum electrodes are investigated by cyclic voltammetry and impedance measurements. Cyclic voltammograms show three reduction steps: two steps relate to the platinum cation reduction, and one step relates to the hydrogen reduction. Hydrogen is not involved in the reduction of PtCl4, however it enables the formation of nanopores in the layers. These findings contribute to the understanding of electrochemical growth of nanoporous platinum layers in isopropanol with thickness of 100 nm to 500 nm.
- ItemCharacterisation of S. aureus/MRSA CC1153 and review of mobile genetic elements carrying the fusidic acid resistance gene fusC([London] : Macmillan Publishers Limited, part of Springer Nature, 2021) Monecke, Stefan; Müller, Elke; Braun, Sascha D.; Armengol-Porta, Marc; Bes, Michèle; Boswihi, Samar; El-Ashker, Maged; Engelmann, Ines; Gawlik, Darius; Gwida, Mayada; Hotzel, Helmut; Nassar, Rania; Reissig, Annett; Ruppelt-Lorz, Antje; Senok, Abiola; Somily, Ali M.; Udo, Edet E.; Ehricht, RalfWhile many data on molecular epidemiology of MRSA are available for North America, Western Europe and Australia, much less is known on the distribution of MRSA clones elsewhere. Here, we describe a poorly known lineage from the Middle East, CC1153, to which several strains from humans and livestock belong. Isolates were characterised using DNA microarrays and one isolate from the United Arab Emirates was sequenced using Nanopore technology. CC1153 carries agr II and capsule type 5 genes. Enterotoxin genes are rarely present, but PVL is common. Associated spa types include t504, t903 and t13507. PVL-positive CC1153-MSSA were found in Egyptian cattle suffering from mastitis. It was also identified among humans with skin and soft tissue infections in Saudi Arabia, France and Germany. CC1153-MRSA were mainly observed in Arabian Gulf countries. Some isolates presented with a previously unknown SCCmec/SCCfus chimeric element in which a mec B complex was found together with the fusidic acid resistance gene fusC and accompanying genes including ccrA/B-1 recombinase genes. Other isolates carried SCCmec V elements that usually also included fusC. Distribution and emergence of CC1153-MRSA show the necessity of molecular characterization of MRSA that are resistant to fusidic acid. These strains pose a public health threat as they combine resistance to beta-lactams used in hospitals as well as to fusidic acid used in the community. Because of the high prevalence of fusC-positive MRSA in the Middle East, sequences and descriptions of SCC elements harbouring fusC and/or mecA are reviewed. When comparing fusC and its surrounding regions from the CC1153 strain to available published sequences, it became obvious that there are four fusC alleles and five distinct types of fusC gene complexes reminiscent to the mec complexes in SCCmec elements. Likewise, they are associated with different sets of ccrA/B recombinase genes and additional payload that might include entire mec complexes or SCCmec elements.
- ItemInfluence of plasma treatment on SiO2/Si and Si3N4/Si substrates for large-scale transfer of graphene([London] : Macmillan Publishers Limited, part of Springer Nature, 2021) Lukose, R.; Lisker, M.; Akhtar, F.; Fraschke, M.; Grabolla, T.; Mai, A.; Lukosius, M.One of the limiting factors of graphene integration into electronic, photonic, or sensing devices is the unavailability of large-scale graphene directly grown on the isolators. Therefore, it is necessary to transfer graphene from the donor growth wafers onto the isolating target wafers. In the present research, graphene was transferred from the chemical vapor deposited 200 mm Germanium/Silicon (Ge/Si) wafers onto isolating (SiO2/Si and Si3N4/Si) wafers by electrochemical delamination procedure, employing poly(methylmethacrylate) as an intermediate support layer. In order to influence the adhesion properties of graphene, the wettability properties of the target substrates were investigated in this study. To increase the adhesion of the graphene on the isolating surfaces, they were pre-treated with oxygen plasma prior the transfer process of graphene. The wetting contact angle measurements revealed the increase of the hydrophilicity after surface interaction with oxygen plasma, leading to improved adhesion of the graphene on 200 mm target wafers and possible proof-of-concept development of graphene-based devices in standard Si technologies.
- ItemMagnetocaloric performance of the three-component Ho1-xErxNi2 (x = 0.25, 0.5, 0.75) Laves phases as composite refrigerants([London] : Macmillan Publishers Limited, part of Springer Nature, 2022) Ćwik, Jacek; Koshkid’ko, Yurii; Nenkov, Konstantin; Tereshina-Chitrova, Evgenia; Małecka, Małgorzata; Weise, Bruno; Kowalska; KarolinaTo date, significant efforts have been put into searching for materials with advanced magnetocaloric properties which show promise as refrigerants and permit realization of efficient cooling. The present study, by an example of Ho1−xErxNi2, develops the concept of magnetocaloric efficiency in the rare-earth Laves-phase compounds. Based on the magneto-thermodynamic properties, their potentiality as components of magnetocaloric composites is illustrated. The determined regularities in the behaviour of the heat capacity, magnetic entropy change, and adiabatic temperature change of the system substantiate reaching high magnetocaloric potentials in a desired temperature range. For the Ho1−xErxNi2 solid solutions, we simulate optimal molar ratios and construct the composites used in magnetic refrigerators performing an Ericsson cycle at low temperatures. The tailored magnetocaloric characteristics are designed and efficient procedures for their manufacturing are developed. Our calculations based on the real empirical data are very promising and open avenue to further experimental studies. Systems showing large magnetocaloric effect (MCE) at low temperatures are of importance due to their potential utilization in refrigeration for gas liquefaction.
- ItemPhenotypic, Morphological and Adhesive Differences of Human Hematopoietic Progenitor Cells Cultured on Murine versus Human Mesenchymal Stromal Cells([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Reichert, Doreen; Friedrichs, Jens; Ritter, Steffi; Käubler, Theresa; Werner, Carsten; Bornhäuser, Martin; Corbeil, DenisXenogenic transplantation models have been developed to study human hematopoiesis in immunocompromised murine recipients. They still have limitations and therefore it is important to delineate all players within the bone marrow that could account for species-specific differences. Here, we evaluated the proliferative capacity, morphological and physical characteristics of human CD34+ hematopoietic stem and progenitor cells (HSPCs) after co-culture on murine or human bone marrow-derived mesenchymal stromal cells (MSCs). After seven days, human CD34+CD133– HSPCs expanded to similar extents on both feeder layers while cellular subsets comprising primitive CD34+CD133+ and CD133+CD34– phenotypes are reduced fivefold on murine MSCs. The number of migrating HSPCs was also reduced on murine cells suggesting that MSC adhesion influences cellular polarization of HSPC. We used atomic force microscopy-based single-cell force spectroscopy to quantify their adhesive interactions. We found threefold higher detachment forces of human HSPCs from murine MSCs compared to human ones. This difference is related to the N-cadherin expression level on murine MSCs since its knockdown abolished their differential adhesion properties with human HSPCs. Our observations highlight phenotypic, morphological and adhesive differences of human HSPCs when cultured on murine or human MSCs, which raise some caution in data interpretation when xenogenic transplantation models are used.
- ItemA tale of shifting relations: East Asian summer and winter monsoon variability during the Holocene([London] : Macmillan Publishers Limited, part of Springer Nature, 2021) Kaboth-Bahr, Stefanie; Bahr, André; Zeeden, Christian; Yamoah, Kweku A.; Lone, Mahjoor Ahmad; Chuang, Chih-Kai; Löwemark, Ludvig; Wei, Kuo-YenUnderstanding the dynamics between the East Asian summer (EASM) and winter monsoon (EAWM) is needed to predict their variability under future global warming scenarios. Here, we investigate the relationship between EASM and EAWM as well as the mechanisms driving their variability during the last 10,000 years by stacking marine and terrestrial (non-speleothem) proxy records from the East Asian realm. This provides a regional and proxy independent signal for both monsoonal systems. The respective signal was subsequently analysed using a linear regression model. We find that the phase relationship between EASM and EAWM is not time-constant and significantly depends on orbital configuration changes. In addition, changes in the Atlantic Meridional Overturning circulation, Arctic sea-ice coverage, El Niño-Southern Oscillation and Sun Spot numbers contributed to millennial scale changes in the EASM and EAWM during the Holocene. We also argue that the bulk signal of monsoonal activity captured by the stacked non-speleothem proxy records supports the previously argued bias of speleothem climatic archives to moisture source changes and/or seasonality.
- ItemSystematic evaluation of particle loss during handling in the percutaneous transluminal angioplasty for eight different drug-coated balloons([London] : Macmillan Publishers Limited, part of Springer Nature, 2020) Heinrich, Andreas; Engler, Martin S.; Güttler, Felix V.; Matthäus, Christian; Popp, Jürgen; Teichgräber, Ulf K.-M.Paclitaxel drug coated balloons (DCBs) should provide optimal drug transfer exclusively to the target tissue. The aim of this study was to evaluate the particle loss by handling during angioplasty. A robotic arm was developed for systematic and reproducible drug abrasion experiments. The contact force on eight different commercially available DCB types was gradually increased, and high-resolution microscopic images of the deflated and inflated balloons were recorded. Three types of DCBs were classified: no abrasion of the drug in both statuses (deflated and inflated), significant abrasion only in the inflated status, and significant abrasion in both statuses. Quantitative measurements via image processing confirmed the qualitative classification and showed changes of the drug area between 2.25 and 45.73% (13.28 ± 14.29%) in the deflated status, and between 1.66 and 40.41% (21.43 ± 16.48%) in the inflated status. The structures and compositions of the DCBs are different, some are significantly more susceptible to drug loss. Particle loss by handling during angioplasty leads to different paclitaxel doses in the target regions for same DCB types. Susceptibility to involuntary drug loss may cause side effects, such as varying effective paclitaxel doses, which may explain variations in studies regarding the therapeutic outcome.
- ItemWorldwide variations in artificial skyglow([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Kyba, Christopher C.M.; Tong, Kai Pong; Bennie, Jonathan; Birriel, Ignacio; Birriel, Jennifer J.; Cool, Andrew; Danielsen, Arne; Davies, Thomas W.; den Outer, Peter N.; Edwards, William; Ehlert, Rainer; Falchi, Fabio; Fischer, Jürgen; Giacomelli, Andrea; Giubbilini, Francesco; Haaima, Marty; Hesse, Claudia; Heygster, Georg; Hölker, Franz; Inger, Richard; Jensen, Linsey J.; Kuechly, Helga U.; Kuehn, John; Langill, Phil; Lolkema, Dorien E.; Nagy, Matthew; Nievas, Miguel; Ochi, Nobuaki; Popow, Emil; Posch, Thomas; Puschnig, Johannes; Ruhtz, Thomas; Schmidt, Wim; Schwarz, Robert; Schwope, Axel; Spoelstra, Henk; Tekatch, Anthony; Trueblood, Mark; Walker, Constance E.; Weber, Michael; Welch, Douglas L.; Zamorano, Jaime; Gaston, Kevin J.Despite constituting a widespread and significant environmental change, understanding of artificial nighttime skyglow is extremely limited. Until now, published monitoring studies have been local or regional in scope and typically of short duration. In this first major international compilation of monitoring data we answer several key questions about skyglow properties. Skyglow is observed to vary over four orders of magnitude, a range hundreds of times larger than was the case before artificial light. Nearly all of the study sites were polluted by artificial light. A non-linear relationship is observed between the sky brightness on clear and overcast nights, with a change in behavior near the rural to urban landuse transition. Overcast skies ranged from a third darker to almost 18 times brighter than clear. Clear sky radiances estimated by the World Atlas of Artificial Night Sky Brightness were found to be overestimated by ~25%; our dataset will play an important role in the calibration and ground truthing of future skyglow models. Most of the brightly lit sites darkened as the night progressed, typically by ~5% per hour. The great variation in skyglow radiance observed from site-to-site and with changing meteorological conditions underlines the need for a long-term international monitoring program.