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51.
Dr. Patrick Feicht Dr. Johannes Biskupek Dr. Tatiana E. Gorelik Julian Renner Dr. Christian E. Halbig Maria Maranska Florian Puchtler Prof. Dr. Ute Kaiser Prof. Dr. Siegfried Eigler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(38):8955-8959
Synthesis and studies of graphite oxide started more than 150 years ago and turned into a boom by the measurements of the outstanding physical properties of graphene. A series of preparation protocols emanated trying to optimize the synthesis of graphene oxide in order to obtain a less defective material, as source for graphene. However, over-oxidation of the carbon framework hampered establishing structure-property relationships. Here, the fact that two different synthetic methods for graphene oxide preparation lead to very similar types of graphene oxide with a preserved graphene lattice is demonstrated. Either sodium chlorate in nitric acid (similar to Brodie's method) or potassium permanganate in sulfuric acid (similar to Hummers’ method) treatment are possible; however, reaction conditions must be controlled. With a preserved carbon lattice analytical differences between the samples relate to the altered on-plane functionality. Consequently, terming preparation protocols “according to Brodie's/Hummers’ method” is not sufficient. 相似文献
52.
Andreas Christoforow Julian Wilke Aylin Binici Axel Pahl Claude Ostermann Sonja Sievers Herbert Waldmann 《Angewandte Chemie (International ed. in English)》2019,58(41):14715-14723
Natural products (NPs) inspire the design and synthesis of novel biologically relevant chemical matter, for instance through biology‐oriented synthesis (BIOS). However, BIOS is limited by the partial coverage of NP‐like chemical space by the guiding NPs. The design and synthesis of “pseudo NPs” overcomes these limitations by combining NP‐inspired strategies with fragment‐based compound design through de novo combination of NP‐derived fragments to unprecedented compound classes not accessible through biosynthesis. We describe the development and biological evaluation of pyrano‐furo‐pyridone (PFP) pseudo NPs, which combine pyridone‐ and dihydropyran NP fragments in three isomeric arrangements. Cheminformatic analysis indicates that the PFPs reside in an area of NP‐like chemical space not covered by existing NPs but rather by drugs and related compounds. Phenotypic profiling in a target‐agnostic “cell painting” assay revealed that PFPs induce formation of reactive oxygen species and are structurally novel inhibitors of mitochondrial complex I. 相似文献
53.
Julian P. Edwards William J. Wolf Robert H. Grubbs 《Journal of polymer science. Part A, Polymer chemistry》2019,57(3):228-242
Cyclic polymers have drawn considerable interest for their peculiar physical properties in comparison to linear polymers, despite their equivalent compositions. Synthetically, cyclic polymers can be accessed through either macrocyclic ring‐closure or by ring‐expansion polymerization, but the main challenge with either method is the production of highly pure cyclic polymer samples. This highlight describes advances in the area of cyclic polymer synthesis, with a particular focus on ring‐expansion metathesis polymerization. Methods for characterizing cyclic polymers and assessing their purity are also discussed in order to emphasize the need for additional robust and reliable methods for synthesizing and studying topologically complex macromolecules. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 228–242 相似文献
54.
In this contribution we propose a simple model of adsorption of a binary (racemic) mixture on a chiraly templated surface. As an example, the adsorption of a liquid mixture of enantiomers on a chiral stationary phase (CSP) is considered. In particular, we study the effect of the lateral interactions in the adsorbed phase on the kinetic and equilibrium isotherms of the enantiomers. Additionally, we investigate the influence of the composition of the surface on the performance of the CSP in the presence of the lateral interactions. To that end, the adsorption of the mixture is modeled by using Monte Carlo simulations as well as by applying an analytical approach involving rate equations coupled with the Mean Field Approximation (MFA). The predictions of the theory are found to be in good agreement with the results of the simulations. 相似文献
55.
d,l-Norleucine is one of only a few molecules whose crystals exhibit a martensitic or displacive-type phase transformation where the emerging phase shows a topotaxial relationship with the parent phase. The molecular mechanism for such phase transformations, particularly in molecular crystals, is not well understood. Crystalline phases that exhibit displacive phase transitions tend to be very similar in structure and energy. Consequently, the development of a force field for such phases is challenging as the phase behavior is determined by subtle differences in their lattice energies and entropies. We report an approach for developing a force field for such phases with an application to d,l-norleucine. The proposed procedure includes calculation of the phase diagram of the crystalline phases as a function of temperature to identify the best force field. d,l-Norleucine also presents an additional problem since in the solid state it exists as a zwitterion that is unstable in vacuo and therefore cannot be characterized using high-level ab initio calculations in the gas phase. However, a stable zwitterion could be obtained using Onsager's reaction-field continuum model for a solvent (SCRF) using both Hartree-Fock and density functional theory. A number of force fields and the various sets of partial charges obtained from the SCRF calculations were screened for their ability to reproduce the crystal structures of the two known phases, alpha and beta, of d,l-norleucine. Selected parameter sets were then employed in free energy minimizations to identify the best set on the basis of a correct prediction of the alpha-beta phase transition. The Williams' nonbonded parameters combined with partial charges from SCRF-Polarized Continuum Model calculation were found to reproduce the structures of the phases accurately and also maintained their stability in extended molecular dynamics simulations in the Parrinello-Rahman constant stress ensemble. Moreover, we were also able to successfully simulate the phase transformation of the beta- to the alpha-phase. The identified force field should enable detailed studies of the phase transformations exhibited by crystals of d,l-norleucine and hence enhance our understanding of martensitic-type transformations in molecular crystals. 相似文献
56.
Ying Su Christos S. Karamitros Julian Nomme Theresa McSorley Manfred Konrad Arnon Lavie 《Chemistry & biology》2013,20(4):533-540
Highlights? Increased expression of hASNase3 was observed in several tumors, but the relevance is unclear ? Cancer cells have increased glycolytic flux and thus have more glycine but less aspartate ? Glycine activates the asparaginase activity of hASNase3 by promoting self-cleavage ? Thus, glycine may act as a sensor that regulates cellular aspartate concentrations 相似文献
57.
Sagisaka M Iwama S Yoshizawa A Mohamed A Cummings S Eastoe J 《Langmuir : the ACS journal of surfaces and colloids》2012,28(30):10988-10996
A previous study (Langmuir2011, 27, 5772) found the fluorinated double-tail sulfogulutarate 8FG(EO)(2) to act as a superefficient solubilizer for water in supercritical CO(2) (W/CO(2)) microemulsions. To explore more economic CO(2)-philic surfactants with high solubilizing power as well as rapid solubilization rates, the effects of fluorocarbon chain length and linking group were examined with sodium 1,5-bis(1H,1H,2H,2H-perfluoroalkyloxy)-1,5-dioxopentane-2-sulfonates (nFG(EO)(2), fluorocarbon chain length n = 4, 6, 8) and sodium 1,4-bis(1H,1H,2H,2H-perfluoroalkyloxy)-1,4-dioxobutane-2-sulfonate (nFS(EO)(2), n = 4, 8). Visual observation and UV-vis spectral measurements with methyl orange as a reporter dye indicated a maximum water-to-surfactant molar ratio (W(0)) in the microemulsions, which was 60-80 for nFG(EO)(2) and 40-50 for nFG(EO)(2). Although it is normally expected that high solubilizing power requires long fluorocarbon surfactant chains, the shortest fluorocarbon 4FG(EO)(2) interestingly achieved the highest W(0) (80) transparent single-phase W/CO(2) microemulsion. In addition, a very rapid solubilization of loaded water into CO(2) was observed for 4FG(EO)(2) even at a high W(0) of ~80. 相似文献
58.
Julian M. Menter George D. Williamson Kimberly Carlyle Cyril L. Moore Isaac Willis 《Photochemistry and photobiology》1995,62(3):402-408
Although previous studies have demonstrated that the predominant photochemistry of type I collagen under 254 nm irradiation may be attributed either to direct absorption by tyrosine/phenylalanine or to peptide bonds, direct collagen photochemistry via solar UV wavelengths is much more likely to involve several age- and tissue-related photolabile collagen fluorophores that absorb in the latter region. In this study, we compare and contrast results obtained from irradiation of a commercial preparation of acid-soluble calf skin type I collagen in solution with UVC (primarily 254 nm), UVA (335–400nm) and broad-band solar-simulating radiation (SSR; 290^1–00nm). Excitation spectroscopy and analysis of photochemically induced disappearance of fluorescence (fluorescence fading) indicates that this preparation has at least four photolabile fluorescent chromophores. In addition to tyrosine and L-3,4-dihydroxyphenylalanine, our sample contains two other fluorophores. Chromophore I, with emission maximum at 360 nm, appears to be derived from interacting aromatic moieties in close mutual proximity. Chromophore II, with broad emission at430–435 nm, may be composed of one or more age-related molecules. Collagen fluorescence fading kinetics are sensitive to excitation wavelength and to conformation. Under UVC, chromophore I fluorescence disappears with second-order kinetics, indicating a reaction between two proximal like molecules. Adherence to second-order kinetics is abrogated by prior denaturation of the collagen sample. A new broad, weak fluorescence band at400–420 nm, attributable to dityrosine, forms under UVC, but not under solar radiation. This band is photolabile to UVA and UVB wavelengths. Amino acid analysis indicates significant destruction of aromatic amino acids under UVC, but not under UVA or SSR. When properly understood, collagen fluorescence fading phenomena may act as a sensitive molecular probe of structure, conformation and reactivity. 相似文献
59.
R. K. Julian M. Nappi C. Weil R. G. Cooks 《Journal of the American Society for Mass Spectrometry》1995,6(1):57-70
A PC-based program that simulates the behavior of a collection of ions is extended to include the effects of collisions with the buffer gas and enhanced visualization methods. The simulations are based on the quadrupole field associated with the actual ion trap electrode structure. Ionization is simulated in such a way as to distribute ionization events randomly over rf phase angles and yield a realistic collection of stored ions. The effects of buffer gas collisions on ion motion during both mass-selective instability and resonance ejection scans are found to include the expected dampening of spatial excursions as well as limitation of the kinetic energy of trapped ions. In both experiments, ion ejection occurs over a number of secular cycles in the vicinity of the theoretical instability point. Activation via a resonant ac signal or a short dc pulse is shown to result in phase-locking of the ions as well as the expected increase in the size of the excursions in the z direction and in ion kinetic energy. Collisions cause dephasing and loss of kinetic energy. Radial dc activation is compared with activation in the axial direction. Experimental data for dc pulse activation of the n-butylbenzene molecular ion are analyzed in phase space and the onset of surface-induced dissociation is correlated with changes in the experimental m/z 91 to m/z 92 fragment ion ratio. Poincaré sections are shown for resonantly excited ions and their value in demonstrating improvement of the resolution of these experiments over conventional mass-selective instability scans is shown. 相似文献
60.
The title amines were pyrolyzed in a stirred-flow reactor at 380–510°C, pressures of 8–15 torr and residence times of 0.3–2.4 s, using toluene as carrier gas. The substrates with an allyl group yielded propene and iminonitriles as reaction products. HCN is formed by decomposition of the iminonitriles. The first-order rate coefficients for propene formation fit the Arrhenius equations
- Allyl cyanomethyl amine:
- Diallyl cyanomethyl amine: