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81.
The structure and properties of optimal networks depend on the cost functional being minimized and on constraints to which the minimization is subject. We show here two different formulations that lead to identical results: minimizing the dissipation rate of an electrical network under a global constraint is equivalent to the minimization of a power-law cost function introduced by Banavar et al. [Phys. Rev. Lett. 84, 4745 (2000)10.1103/PhysRevLett.84.4745]. An explicit scaling relation between the currents and the corresponding conductances is derived, proving the potential flow nature of the latter. Varying a unique parameter, the topology of the optimized networks shows a transition from a tree topology to a very redundant structure with loops; the transition corresponds to a discontinuity in the slope of the power dissipation. 相似文献
82.
Capillary sieving electrophoresis utilizing SDS (CE(SDS)) is one of the most applied methods for the analysis of antibody (mAb) size heterogeneity in the biopharmaceutical industry. Inadequate peak identification of observed protein fragments is still a major issue. In a recent publication, we introduced an electrophoretic 2D system, enabling online mass spectrometric detection of generic CE(SDS) separated peaks and identification of several mAb fragments. However, an improvement regarding system stability and handling of the approach was desired. Here, we introduce a novel 8-port valve in conjunction with an optimized decomplexation strategy. The valve contains four sample loops with increased distances between the separation dimensions. Thus, successively coinjection of solvent and cationic surfactant without any additional detector in the second dimension is enabled, simplifying the decomplexation strategy. Removal efficiency was optimized by testing different volumes of solvents as presample and cationic surfactant as postsample zone. 2D measurements of the light and heavy chain of the reduced NIST mAb with the 8-port valve and the optimized decomplexation strategy demonstrates the increased robustness of the system. The presented novel set-up is a step toward routine application of CE(SDS)-CZE-MS for impurity characterization of proteins in the biopharmaceutical field. 相似文献
83.
Steffen Dachwitz Bjarne Scharkowski Prof. Norbert Sewald 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(72):18043-18046
Mild transition-metal catalysed cross-couplings enable direct functionalisation of biocatalytically halogenated tryptophans with alkyl iodides, representing a new alternative for late-stage derivatisations of halogenated aromatic amino acids. Moreover, this strategy enables preparation of (homo)tryptophan regioisomers in a simple two-step synthesis using a Pd-catalysed Negishi cross coupling. This method provides access to non-canonical constitutional surrogates of tryptophan, ready for use in peptide synthesis. 相似文献
84.
85.
Eckhard Steffen 《Journal of Graph Theory》2015,78(3):195-206
Let G be a bridgeless cubic graph. Consider a list of k 1‐factors of G. Let be the set of edges contained in precisely i members of the k 1‐factors. Let be the smallest over all lists of k 1‐factors of G. Any list of three 1‐factors induces a core of a cubic graph. We use results on the structure of cores to prove sufficient conditions for Berge‐covers and for the existence of three 1‐factors with empty intersection. Furthermore, if , then is an upper bound for the girth of G. We also prove some new upper bounds for the length of shortest cycle covers of bridgeless cubic graphs. Cubic graphs with have a 4‐cycle cover of length and a 5‐cycle double cover. These graphs also satisfy two conjectures of Zhang 18 . We also give a negative answer to a problem stated in 18 . 相似文献
86.
Regiospecific Formation and Unusual Optical Properties of 2,5‐Bis(arylethynyl)rhodacyclopentadienes: A New Class of Luminescent Organometallics 下载免费PDF全文
Dr. Andreas Steffen Dr. Richard M. Ward Dr. Meng Guan Tay Dr. Robert M. Edkins Dr. Fabian Seeler Magda van Leeuwen Dr. Lars‐Olof Pålsson Prof. Dr. Andrew Beeby Dr. Andrei S. Batsanov Prof. Dr. Judith A. K. Howard Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(13):3652-3666
A series of 2,5‐bis(arylethynyl)rhodacyclopentadienes has been prepared by a rare example of regiospecific reductive coupling of 1,4‐(p‐R‐phenyl)‐1,3‐butadiynes (R?H, Me, OMe, SMe, NMe2, CF3, CO2Me, CN, NO2, ?C?C‐(p‐C6H4?NHex2), ?C?C?(p‐C6H4?CO2Oct)) at [RhX(PMe3)4] ( 1 ) (X=?C?C?SiMe3 ( a ), ?C?C‐(p‐C6H4?NMe2) ( b ), ?C?C?C?C?(p‐C6H4?NPh2) ( c ) or ?C?C?{p‐C6H4‐C?C?(p‐C6H4‐N(C6H13)2)} ( d ) or Me ( e )), giving the 2,5‐bis(arylethynyl) isomer exclusively. The rhodacyclopentadienes bearing a methyl ligand in the equatorial plane (compound 1 e ) have been converted into their chloro analogues by reaction with HCl etherate. The rhodacycles thus obtained are stable to air and moisture in the solid state and the acceptor‐substituted compounds are even stable to air and moisture in solution. The photophysical properties of the rhodacyclopentadienes are highly unusual in that they exhibit, exclusively, fluorescence between 500–800 nm from the S1 state, with quantum yields of Φ=0.01–0.18 and short lifetimes (τ=0.45–8.20 ns). The triplet state formation (ΦISC=0.57 for 2 a ) is exceptionally slow, occurring on the nanosecond timescale. This is unexpected, because the Rh atom should normally facilitate intersystem crossing within femto‐ to picoseconds, leading to phosphorescence from the T1 state. This work therefore highlights that in some transition‐metal complexes, the heavy atom can play a more subtle role in controlling the photophysical behavior than is commonly appreciated. 相似文献
87.
A Deadly Organometallic Luminescent Probe: Anticancer Activity of a ReI Bisquinoline Complex 下载免费PDF全文
Dr. Igor Kitanovic Suzan Can Dr. Hamed Alborzinia Dr. Ana Kitanovic Vanessa Pierroz Anna Leonidova Dr. Antonio Pinto Priv. Doz. Dr. Bernhard Spingler Priv. Doz. Dr. Stefano Ferrari Roberto Molteni Dr. Andreas Steffen Prof. Dr. Nils Metzler‐Nolte Prof. Dr. Stefan Wölfl Prof. Dr. Gilles Gasser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(9):2496-2507
The photophysical properties of [Re(CO)3(L ‐N3)]Br (L ‐N3=2‐azido‐N,N‐bis[(quinolin‐2‐yl)methyl]ethanamine), which could not be localized in cancer cells by fluorescence microscopy, have been revisited in order to evaluate its use as a luminescent probe in a biological environment. The ReI complex displays concentration‐dependent residual fluorescence besides the expected phosphorescence, and the nature of the emitting excited states have been evaluated by DFT and time‐dependent (TD) DFT methods. The results show that fluorescence occurs from a 1LC/MLCT state, whereas phosphorescence mainly stems from a 3LC state, in contrast to previous assignments. We found that our luminescent probe, [Re(CO)3(L ‐N3)]Br, exhibits an interesting cytotoxic activity in the low micromolar range in various cancer cell lines. Several biochemical assays were performed to unveil the cytotoxic mechanism of the organometallic ReI bisquinoline complex. [Re(CO)3(L ‐N3)]Br was found to be stable in human plasma indicating that [Re(CO)3(L ‐N3)]Br itself and not a decomposition product is responsible for the observed cytotoxicity. Addition of [Re(CO)3(L ‐N3)]Br to MCF‐7 breast cancer cells grown on a biosensor chip micro‐bioreactor immediately led to reduced cellular respiration and increased glycolysis, indicating a large shift in cellular metabolism and inhibition of mitochondrial activity. Further analysis of respiration of isolated mitochondria clearly showed that mitochondrial respiratory activity was a direct target of [Re(CO)3(L ‐N3)]Br and involved two modes of action, namely increased respiration at lower concentrations, potentially through increased proton transport through the inner mitochondrial membrane, and efficient blocking of respiration at higher concentrations. Thus, we believe that the direct targeting of mitochondria in cells by [Re(CO)3(L ‐N3)]Br is responsible for the anticancer activity. 相似文献
88.
Kay Hettrich Manfred Pinnow Bert Volkert Lars Passauer Steffen Fischer 《Cellulose (London, England)》2014,21(4):2479-2488
Novel nanoscaled cellulose particles were prepared using high-pressure homogenization of aqueous media contenting treated cellulose samples in a Microfluidizer® processor (MF). Here, we present the generation of spherical cellulose nanoparticles as an extension of previously published reports of nano fibrillated cellulose. Although MF treatment of unmodified cellulose yields nanofibrils which are reported in several publications, in the current work different kinds of pretreatments were proven to be necessary to obtain spherical structured cellulose nanoparticles. One such treatment may be the decrystallization of cellulose regenerating it from N-methylmorpholine-N-oxid-monohydrate (NMMNO*H2O). Nanocellulose was then obtained by a subsequent high-pressure mechanical treatment of the precipitate in aqueous dispersion. Decrystallization was also realized by grinding cellulose in a planetary ball mill. The resulting amorphous intermediates were characterized by Raman spectroscopy. Another approach tested was hydrolysis and subsequent mechanical treatment using an Ultra-Turrax® and MF. Another alternative was given by the mechanical treatment of aqueous dispersions of low substituted cellulose derivatives such as carboxymethyl cellulose and oxidized cellulose without any further hydrolysis. 相似文献
89.
Agus R. Poerwoprajitno Dr. Lucy Gloag Dr. John Watt Steffen Cychy Dr. Soshan Cheong Dr. Priyank V. Kumar Dr. Tania M. Benedetti Chen Deng Dr. Kuang-Hsu Wu Dr. Christopher E. Marjo Dr. Dale L. Huber Dr. Martin Muhler Prof. Dr. J. Justin Gooding Prof. Dr. Wolfgang Schuhmann Prof. Dr. Da-Wei Wang Prof. Dr. Richard D. Tilley 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(36):15615-15620
90.
The stannides RE2Au3Sn6 (RE = La, Ce, Pr, Nd, Sm) were synthesized from the elements by arc-melting. Small single crystals were grown by annealing samples in sealed tantalum tubes in an induction furnace with a special annealing sequence. The polycrystalline phases were characterized through their X-ray powder diffraction pattern. The structures of Ce2Au3Sn6, Pr2Au3Sn6, and Nd2Au3Sn6 were refined from single-crystal X-ray diffractometer data. The RE2Au3Sn6 stannides crystallize with the orthorhombic La2Zn3Ge6 type, space group Cmcm. The basic structural building units are Au1@Sn4 tetrahedra and Au2@Sn5 square pyramids. These units are condensed to layers and the structure can be described by a simple stacking of tetrahedral and pyramidal layers with the rare earth cations in between. Temperature dependent susceptibility studies indicate that all rare earth atoms are in the trivalent oxidation state, as their effective magnetic moments match the expected values of the free RE3+ ions. Pr2Au3Sn6 and Nd2Au3Sn6 exhibit antiferromagnetic ordering at TN = 6.3(1) and 6.7(1) K. Investigations of the electrical resistivity of La2Au3Sn6 and Ce2Au3Sn6 confirmed that these compounds are metallic, for La2Au3Sn6 a lower resistivity was observed, in line with the absence of screening unpaired electrons. 119Sn Mössbauer spectra for La2Au3Sn6, Ce2Au3Sn6, Pr2Au3Sn6 and Nd2Au3Sn6 show a complex superposition of three sub-spectra which can be differentiated through their distinctly different quadrupole splitting parameters. The isomer shifts (1.87 to 2.22 mm · s–1) indicate significant s electron density at the tin nuclei. 相似文献