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731.
Katrin Krüger Virginia Lüdke Jonathan Pettinger Luke Ashton Laetitia Bonnet Cherie A. Motti Johann Lex Michael Oelgemöller 《Tetrahedron letters》2018,59(14):1427-1430
The photochemistry of several phthalimido acetamides and phthaloyl dipeptide esters has been investigated. Their photocyclization ability strongly depended on the substitution pattern of the amide linker group. While secondary amide-derived starting materials were largely unreactive, the corresponding tertiary amide-linked derivatives furnished the desired cyclic peptide model compounds in acceptable to good yields (41–80%). The structurally related ester-linked model derivatives also remained unreactive upon irradiation. Preferential hydrogen-abstraction from the E-cis-substituent is suggested to explain the observed differences in cyclization ability. 相似文献
732.
Dr. Toyoto Sato Dr. Luke L. Daemen Dr. Yongqiang Cheng Dr. Anibal J. Ramirez-Cuesta Dr. Kazutaka Ikeda Takuma Aoki Dr. Toshiya Otomo Prof. Shin-ichi Orimo 《Chemphyschem》2019,20(10):1392-1397
The hydrogen-release reaction of a complex transition metal hydride, LaMg2NiH7, composed of La3+, 2×Mg2+, [NiH4]4− and 3×H−, was studied by thermal analyses, powder X-ray, and neutron diffraction and inelastic neutron scattering. Upon heating, LaMg2NiH7 released hydrogen at approximately 567 K and decomposed into LaH2−3 and Mg2Ni. Before the reaction, covalently bound hydrogen (Hc°v.) in [NiH4]4− exhibited a larger atomic displacement than H−, although a weakening of the chemical bonds around [NiH4]4− and H− was observed. These results indicate the precursor phenomenon of a hydrogen-release reaction, wherein there is a large atomic displacement of Hc°v. that induces the hydrogen-release reaction rather than H−. As an isothermal reaction, LaMg2NiH7 formed LaMg2NiH2.4 at 503 K in vacuum for 48 h, and LaMg2NiH2.4 reacted with hydrogen to reform LaMg2NiH7 at 473 K under 1 MPa of H2 gas pressure for 10 h. These results revealed that LaMg2NiH7 exhibited partially reversible hydrogen-release and uptake reactions. 相似文献
733.
The distinguishing number of
$$G \leqslant \mathrm {Sym}(\Omega )$$
is the smallest size of a partition of
$$\Omega $$
such that only the identity of G fixes all the parts of the partition. Extending earlier results of Cameron, Neumann, Saxl, and Seress on the distinguishing number of finite primitive groups, we show that all imprimitive quasiprimitive groups have distinguishing number two, and all non-quasiprimitive semiprimitive groups have distinguishing number two, except for
$$\mathrm {GL}(2,3)$$
acting on the eight non-zero vectors of
$$\mathbb {F}_3^2$$
, which has distinguishing number three. 相似文献
734.
Zuzana Kotková Dr. Jan Kotek Dr. Daniel Jirák Dr. Pavla Jendelová Dr. Vít Herynek Dr. Zuzana Berková Dr. Petr Hermann Dr. Ivan Lukeš Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(33):10094-10102
A novel bimodal fluorescence/MRI probe based on a cyclodextrin scaffold has been synthesized and characterized. The final agent employs the fluorescein (F) functionality as a fluorescence marker and the GdIII complex of a macrocyclic DOTA‐based ligand (GdL) having one aminobenzyl‐phosphinic acid pendant arm as an MRI probe, and has a statistical composition of (GdL)6.9‐F0.1‐β‐CD. Slow rotational dynamics (governed by a very rigid cyclodextrin scaffold) combined with fast water exchange (ensured by the chosen macrocyclic ligand) resulted in a high relaxivity of ~22 s?1 mM ?1 per GdIII or ~150 s?1 mM ?1 per molecule of the final conjugate (20 MHz, 25 °C). In vitro labelling of pancreatic islets (PIs) and rat mesenchymal stem cells has been successfully performed. The agent is not cytotoxic and is easily internalized into cells. The labelled cells can be visualized by MRI, as proved by the detection of individual labelled PIs. A fluorescence study performed on mesenchymal stem cells showed that the agent stays in the intracellular space for a long time. 相似文献
735.
Charles Acquah Arunprakash T. Karunanithi Matthew Cagnetta Luke E.K. Achenie Steven L. Suib 《Fluid Phase Equilibria》2009
Solvents have a significant impact on the final crystal form of organic solids during solution crystallization. The use of polarity scales such as Hildebrand solubility parameter and dielectric constant for solvent selection often proves too generalized and do not provide enough insights into the solvent–solute intermolecular interactions directly affecting crystal growth and morphology. This paper addresses the challenging task of selecting an appropriate single component solvent property index that most accurately and sufficiently characterizes crystal morphology. Cooling crystallization experiments were carried out in a wide range of solvents using ibuprofen as a model pharmaceutical compound. Subsequently, optical microscope images were used for quantitative characterization of morphology. Linear models that correlate ibuprofen crystal morphology with pure solvent properties were developed. Our results show that, in general, there is a negative linear correlation between crystal aspect ratio (morphology) and a given solvent index. Some correlations revealed significant deviations which were explained with the help of infrared spectroscopic measurements. The “acceptance number” was identified as an index that significantly captures the ibuprofen–solvent hydrogen bonding intermolecular interactions. Predictions, using model based on acceptance number, were found to compare very well with experimentally determined aspect ratio data from the open literature. Finally, based on insights gained from this work, a flowchart which serves as a useful solvent selection guideline for crystallization of ibuprofen is proposed. 相似文献
736.
Burrell AJ Coldham I Watson L Oram N Pilgram CD Martin NG 《The Journal of organic chemistry》2009,74(6):2290-2300
The preparation of tricyclic amines from acyclic precursors is described using a cascade of tandem reactions involving condensation of an aldehyde with a primary amine, cyclization (with displacement of a halide), and then in situ deprotonation or decarboxylation to give an azomethine ylide or nitrone followed by intramolecular dipolar cycloaddition. The methodology is straightforward, and the aldehyde precursors are prepared easily and quickly in high yield using nitrile alkylations followed by DIBAL-H reduction. The relative ease of reaction of various substrates with different tether lengths between the aldehyde and the halide or dipolarophile has been studied. Several primary amines including simple amino acids such as glycine, alanine, and phenylalanine and derivatives such as glycine ethyl ester and also hydroxylamine have been investigated. High yields are obtained in the formation of different tricyclic ring sizes; the dipolar cycloaddition necessarily creates a five-membered ring, and we have investigated the formation of five- and six-membered rings for the other two new ring sizes. In all cases, yields are high (except when using glycine when the tether to the terminal alkene dipolarophile leads to a six-membered ring), and most efficient is the formation of the tricyclic product in which all five-membered rings are formed. Examples with an alkyne as the dipolarophile were also successful. In all the reactions studied, the products are formed with complete regioselectivity and remarkably with complete stereoselectivity. The key step involves the formation of three new rings and potentially up to four new stereocenters in a single transformation. The power of the chemistry was demonstrated by the synthesis of the core ring systems of the alkaloids (+/-)-scandine and (+/-)-myrioneurinol and the total syntheses of the alkaloids (+/-)-aspidospermine, (+/-)-quebrachamine, and (+/-)-aspidospermidine. 相似文献
737.
Michael J. Evans Myeong H. Lee Gregory P. Holland Luke L. Daemen Otto F. Sankey Ulrich Hussermann 《Journal of solid state chemistry》2009,182(8):2068-2073
Vibrational properties of the gallium monohydrides SrGaGeH, BaGaSiH, BaGaGeH, and BaGaSnH (AeGaTtH) have been investigated by means of inelastic neutron scattering (INS) and first principles calculations. The compounds contain separated Ga–H units being part of a two dimensional polyanionic layer, [TtGaH]2− (Tt=Si, Ge, Sn). The INS spectra show internal Ga–H bending and stretching modes at frequencies around 900 and 1200 cm−1, respectively. While the stretching mode is virtually invariant with respect to the variable chemical environment of the Ga–H unit, the bending mode frequency varies and is highest for BaGaSiH and lowest for BaGaSnH. The stretching mode is a direct measure of the Ga–H bond strength, whereas the bending mode reflects indirectly the strength of alkaline earth metal–hydrogen interaction. Accordingly, the terminal Ga–H bond in solid state AeGaTtH is distinct, but—compared to molecular gallium hydrides—very weak. 相似文献
738.
We construct a theory of distributions in the setting of analysis on post-critically finite self-similar fractals, and on
fractafolds and products based on such fractals. The results include basic properties of test functions and distributions,
a structure theorem showing that distributions are locally-finite sums of powers of the Laplacian applied to continuous functions,
and an analysis of the distributions with point support. Possible future applications to the study of hypoelliptic partial
differential operators are suggested. 相似文献
739.
P.C. Canfield S.L. Bud’ko N. Ni A. Kreyssig A.I. Goldman R.J. McQueeney M.S. Torikachvili D.N. Argyriou G. Luke W. Yu 《Physica C: Superconductivity and its Applications》2009,469(9-12):404-412
At ambient pressure CaFe2As2 has been found to undergo a first order phase transition from a high temperature, tetragonal phase to a low-temperature orthorhombic/antiferromagnetic phase upon cooling through T ~ 170 K. With the application of pressure this phase transition is rapidly suppressed and by ~0.35 GPa it is replaced by a first order phase transition to a low-temperature collapsed tetragonal, non-magnetic phase. Further application of pressure leads to an increase of the tetragonal to collapsed tetragonal phase transition temperature, with it crossing room temperature by ~1.7 GPa. Given the exceptionally large and anisotropic change in unit cell dimensions associated with the collapsed tetragonal phase, the state of the pressure medium (liquid or solid) at the transition temperature has profound effects on the low-temperature state of the sample. For He-gas cells the pressure is as close to hydrostatic as possible and the transitions are sharp and the sample appears to be single phase at low temperatures. For liquid media cells at temperatures below media freezing, the CaFe2As2 transforms when it is encased by a frozen media and enters into a low-temperature multi-crystallographic-phase state, leading to what appears to be a strain stabilized superconducting state at low temperatures. 相似文献
740.
Dr. Luke J. O'Driscoll Dr. Daniel J. Welsh Dr. Steven W. D. Bailey Dr. David Visontai Dr. Harry Frampton Prof. Martin R. Bryce Prof. Colin J. Lambert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(10):3891-3894
Easily reversible aqueous dispersion/precipitation of multiwalled carbon nanotubes (MWNTs) has been demonstrated using small‐molecule non‐ionic pyrene‐based surfactants, which exhibit lower critical solution temperature (LCST) phase behaviour. The MWNTs are dispersed by means of non‐covalent interactions. The dispersibility can be switched “off” (i.e., MWNTs precipitated) upon heating and switched “on” (i.e., MWNTs re‐dispersed) upon cooling and merely swirling the sample at room temperature, that is, under very mild conditions. This effect is also observed under high ionic strength conditions with NaCl in the aqueous phase. 相似文献