A metric jet can be linear without being the metric jet of a continuous linear map. We begin with giving such an amazing example and then we get interested in tangentiable maps whose tangent jet at a point is precisely a linear metric jet. For such maps, a local inversion theorem is still true. 相似文献
New redox-active 1,2,5,6-tetrakis(guanidino)-naphthalene compounds, isolable and storable in the neutral and deep-green dicationic redox states and oxidisable further in two one-electron steps to the tetracations, are reported. Protonation switches on blue fluorescence, with the fluorescence intensity (quantum yield) increasing with the degree of protonation. Reactions with N-halogenosuccinimides or N-halogenophthalimides led to a series of new redox-active halogeno- and succinimido-/phthalimido-substituted derivatives. These highly selective reactions are proposed to proceed via the tri- or tetracationic state as the intermediate. The derivatives are oxidised reversibly at slightly higher potentials than that of the unsubstituted compounds to dications and further to tri- and tetracations. The integration of redox-active ligands in the transition-metal complexes shifts the redox potentials to higher values and also allows reversible oxidation in two potentially separated one-electron steps. 相似文献
A series of substituted 3‐azabicyclo[4.1.0]hept‐4‐ene derivatives were prepared and analysed by cyclic voltammetry. Preparative aerobic electrochemical oxidation reactions were then carried out. Three original endoperoxides were isolated, characterised and subjected to antimalarial and cytotoxicity activity assays. 相似文献
Graphene oxide (GO) is a versatile platform with unique properties that have found broad applications in the biomedical field. Double functionalization is a key aspect in the design of multifunctional GO with combined imaging, targeting, and therapeutic properties. Compared to noncovalent functionalization, covalent strategies lead to GO conjugates with a higher stability in biological fluids. However, only a few double covalent functionalization approaches have been developed so far. The complexity of GO makes the derivatization of the oxygenated groups difficult to control. The combination of a nucleophilic epoxide ring opening with the derivatization of the hydroxyl groups through esterification or Williamson reaction was investigated. The conditions were selective and mild, thus preserving the structure of GO. Our strategy of double functionalization holds great potential for different applications in which the derivatization of GO with different molecules is needed, especially in the biomedical field. 相似文献
Microstructure, surface topography, thermal and mechanical features of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) electrospun non-woven mats were modified, modulated and tailored through blending with different polyethylene oxide (PEO) amounts (20, 30 and 50% wt/wt). The optimal parameters of the soaking protocol for the selective removal of the sacrificial polymer were accurately identified by means of scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy, simultaneous thermogravimetric and differential analyses (TG-DTA) and differential scanning calorimetry (DSC). The complete PEO removal after soaking in H2O for 7 days with daily refreshment was confirmed. The resulting samples were only comprised of PHBV fibers characterized by a remarkable decrease of the average size with respect to the respective blends. Their surface topography was corrugated and rough and presented nodules, pits, nanopores, shallow and elongated nanostructured indents/grooves along the fiber axis. A remarkable reduction (>75%) of the tensile modulus (E) of electrospun PHBV mats (15–20 MPa) was obtained, maintaining comparable elongation at break (εmax) values (20–30%). 相似文献
In order to deliver reliable results for a multitude of different scenarios, e.g. emergency preparedness, environmental monitoring, nuclear decommissioning and waste management, there is a constant process of method development in the field of radioanalytical chemistry. This work presents the results of a method comparison exercise aimed at quantifying 90Sr and 239,240Pu in environmental soil samples, with the intention of evaluating the performance and applicability of different methods. From the methods examined in this work, recommendations are given in order to find a radioanalytical measurement procedure, for 90Sr and 239,240Pu analysis, which is fit-for-purpose for a particular scenario.
Two synthetic precursor peptides, H2N-CVGIW and H2N-LVMCCVGIW, involved in the quorum sensing of Lactobacillus plantarum WCFS1, were characterized by mass spectrometry (MS) with electrospray ionization and 7-T Fourier transform ion cyclotron resonance (ESI-FTICR) instrument. Cell-free bacterial supernatant solutions were analyzed by reversed-phase liquid chromatography with ESI-FTICR MS to verify the occurrence of both pentapeptide and nonapeptide in the bacterial broth. The structural characterization of both protonated peptides was performed by infrared multiphoton dissociation using a continuous CO2 laser source at a wavelength of 10.6 μm. As their fragmentation behavior cannot be directly derived from the primary peptide structure, all anomalous fragments were interpreted as neutral loss of amino acids from the interior of both peptides, i.e., loss of V, G, VG and M, MC, V, CC, from H2N-CVGIW and H2N-LVMCCVGIW, respectively. Mechanisms of this scrambling are proposed. FTICR MS provides accurate masses of all fragment ions with very low absolute mass errors (<1.6 ppm), which facilitated the reliable assignment of their elemental compositions. The resolving power was more than sufficient to resolve closely isobaric product ions with routine subparts per million mass accuracies. Only the occurrence of pentapeptide was found in the cell-free culture of L. plantarum, grown in Waymouth’s medium broth, with a low content of 5.2?±?2.6 μM by external calibration. Most of it was present as oxidized H2N-CVGIW, that is, the soluble disulfide pentapeptide with a level tenfold higher (i.e., 50?±?4 μM, n?=?3).
Figure
IRMPD of the precursor protonated peptide, [H2N-CVGIW +H]+ at m/z 577.3 and suggested pathway showing the formation of peptide macrocycle and its selective ring opening. 相似文献