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11.
We study the asymptotic Dirichlet problem for the minimal graph equation on a Cartan–Hadamard manifold M whose radial sectional curvatures outside a compact set satisfy an upper bound
$$\begin{aligned} K(P)\le - \frac{\phi (\phi -1)}{r(x)^2} \end{aligned}$$
and a pointwise pinching condition
$$\begin{aligned} |K(P) |\le C_K|K(P') | \end{aligned}$$
for some constants \(\phi >1\) and \(C_K\ge 1\), where P and \(P'\) are any 2-dimensional subspaces of \(T_xM\) containing the (radial) vector \(\nabla r(x)\) and \(r(x)=d(o,x)\) is the distance to a fixed point \(o\in M\). We solve the asymptotic Dirichlet problem with any continuous boundary data for dimensions \(n=\dim M>4/\phi +1\).
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12.
13.
Liquid chromatography coupled with mass spectrometry for the determination of total and unbound mycophenolic acid and its major metabolite in human plasma has been developed. Sample preparations were based on a fully automated solid-phase extraction process and ultrafiltration. Mass spectrometric data were acquired in a single-ion monitoring method. The analytes and nevirapine (internal standard) were well separated in an isocratic mode over 8 min. Validation study exhibited excellent linearity, with intra- and inter-day precision and accuracy of less than 12%. The assay was successfully applied to the pharmacokinetic study of mycophenolic acid in patients with autoimmune diseases.  相似文献   
14.
    
Hydrosilylation is an important process, not only in the silicon industry to produce silicon polymers, but also in fine chemistry. In this review, the development of rhenium-based catalysts for the hydrosilylation of unsaturated bonds in carbonyl-, cyano-, nitro-, carboxylic acid derivatives and alkenes is summarized. Mechanisms of rhenium-catalyzed hydrosilylation are discussed.  相似文献   
15.
    
The important role that G-quadruplex DNA (G4 DNA) structures play in regulating biological processes is becoming widely recognised. These structures have also been proposed to be attractive drug targets. Therefore, there has been significant interest in developing small molecules that can selectively bind to G4 DNA over other topologies. In this paper we investigate the interaction between DNA and helical compounds (helicenes) based on a central carbocation trisubstituted with aromatic rings. We show that the non-planar structure of these helicenes results in a significantly reduced affinity for dsDNA when compared to their planar analogues, whilst maintaining a high affinity for G4 DNA. Additionally, the right- and left-handed enantiomers of one of these helicenes recognise the chiral DNA environments of G4 and dsDNA differently. We show that upon DNA binding the helicenes display a fluorescence switch-on effect, which we have successfully used for cellular imaging in live and fixed U2OS cells, staining mitochondria and the nucleus, respectively.

G-quadruplex DNA (G4 DNA) structures are selectively recognised by helical optical probes.  相似文献   
16.
Accurate and efficient filtering techniques are required to suppress large nuisance components present in short-echo time magnetic resonance (MR) spectra. This paper discusses two powerful filtering techniques used in long-echo time MR spectral quantitation, the maximum-phase FIR filter (MP-FIR) and the Hankel-Lanczos Singular Value Decomposition with Partial ReOrthogonalization (HLSVD-PRO), and shows that they can be applied to their more complex short-echo time spectral counterparts. Both filters are validated and compared through extensive simulations. Their properties are discussed. In particular, the capability of MP-FIR for dealing with macromolecular components is emphasized. Although this property does not make a large difference for long-echo time MR spectra, it can be important when quantifying short-echo time spectra.  相似文献   
17.
The chemical control of magnetic and conduction properties for organic radicals is mainly based on t, the resonance integral, and U, the on-site repulsion, used in the Hubbard model. A qualitative analysis based on the competition between the kinetic and the Coulomb contribution, and the expression of the magnetic exchange coupling suggests that U should be roughly 800 cm(-1) while the resonance integral |t| should be 200 cm(-1) to reach bifunctionality. Ab initio wavefunction-based calculations allowed us to quantitatively measure those quantities for several organic materials considered as 1D systems starting from their reported crystal structures. The extraction of t and U parameters from the exchange coupling constants between neighbouring radicals allowed us to anticipate a possible metallic behaviour. Finally, the impact of chemical changes in the constitutive units is measured to rationalize the macroscopic behaviour modifications. It is shown that the intriguing regime characterized by simultaneous itinerant and localized electrons might be achieved by molecular engineering.  相似文献   
18.
Framework functionalisation triggers metal complex binding   总被引:1,自引:0,他引:1  
Post-synthetic derivatisation of a porous material produces a functionalized material that binds the metal complex V(O)acac2, in contrast to the unfunctionalized precursor, which is inactive for complex binding.  相似文献   
19.
Cyclodipeptide synthases (CDPSs) are small enzymes structurally related to class-I aminoacyl-tRNA synthetases (aaRSs). They divert aminoacylated tRNAs from their canonical role in ribosomal protein synthesis, for cyclodipeptide formation. All the CDPSs experimentally characterized to date are?bacterial. We show here that a predicted CDPS from the sea anemone Nematostella vectensis is an active CDPS catalyzing the formation of various cyclodipeptides, preferentially containing tryptophan. Our findings demonstrate that eukaryotes encode active CDPSs and suggest that all CDPSs have?a similar aminoacyl-tRNA synthetase-like architecture and ping-pong mechanism. They also raise questions about the biological roles of the cyclodipeptides produced in bacteria and eukaryotes.  相似文献   
20.
Chloride transport by a series of steroid-based "cholapod" receptors/carriers was studied in vesicles. The principal method involved preincorporation of the cholapods in the vesicle membranes, and the use of lucigenin fluorescence quenching to detect inward-transported Cl-. The results showed a partial correlation between anion affinity and transport activity, in that changes at the steroidal 7 and 12 positions affected both properties in concert. However, changes at the steroidal 3-position yielded irregular effects. Among the new steroids investigated the bis-p-nitrophenylthiourea 3 showed unprecedented activity, giving measurable transport through membranes with a transporter/lipid ratio of 1:250 000 (an average of <2 transporter molecules per vesicle). Increasing transporter lipophilicity had no effect, and positively charged steroids had low activity. The p-nitrophenyl monourea 25 showed modest but significant activity. Measurements using a second method, requiring the addition of transporters to preformed vesicle suspensions, implied that transporter delivery was problematic in some cases. A series of measurements employing membranes of different thicknesses provided further evidence that the cholapods act as mobile anion carriers.  相似文献   
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