A method for enhancing positive analyte ion signal in MALDI is described. The idea is based on influencing the kinetic energy of free electrons emitted from the organic/metal interface. It has been recently shown that free electrons in MALDI have energies around 1 eV. This energy is close to the maximum capture cross-section of most common MALDI matrices, leading to the efficient formation of negative matrix ions. This results in the reduction of the positive analyte ion yield. The effect can be minimized by shifting the kinetic energy of the electrons away from the maximum of the matrix capture cross-section by choosing a different substrate material. 相似文献
We present a combined density functional theory (DFT)/time-dependent density functional theory (TDDFT) study of the geometry, electronic structure, and absorption and emission properties of the tetranuclear "cubane" Cu4I4py4 (py = pyridine) system. The geometry of the singlet ground state and of the two lowest triplet states of the title complex were optimized, followed by TDDFT excited-state calculations. This procedure allowed us to characterize the nature of the excited states involved in the absorption spectrum and those responsible for the dual emission bands observed for this complex. In agreement with earlier experimental proposals, we find that while in absorption the halide-to-pyridine charge-transfer excited state (XLCT*) has a lower energy than the cluster-centered excited state (CC*), a strong geometrical relaxation on the triplet cluster-centered state surface leads to a reverse order of the excited states in emission. 相似文献
Sonic spray ionization is shown to create a supersonic cloud of charged droplets able to promote efficient desorption and ionization of drugs directly from the surfaces of commercial drug tablets at ambient conditions. Compared with desorption electrospray ionization (DESI), desorption sonic spray ionization (DeSSI) is advantageous since it uses neither heating nor high voltages at the spray capillary. DeSSI therefore provides a more friendly environment in which to perform ambient mass spectrometry (MS). DeSSI-MS is herein evaluated for the analysis of drug tablets, and found to be, in general, as sensitive as DESI-MS. The (high) voltage-free DeSSI method provides, however, cleaner mass spectra with less abundant solvent cluster ions and with enough abundant analyte signal for tandem mass spectrometry (MS/MS). These features may therefore facilitate the DeSSI-MS detection of low molar mass components or impurities, or both. The higher-velocity supersonic DeSSI spray also facilitates matrix penetration thus providing more homogenous sampling and longer lasting ion signals. 相似文献
By performing density functional theory calculations we show that it is possible to make the electronic bandgap in bilayer graphene supported on hexagonal boron nitride (h-BN) substrates tunable. We also show that, under applied electric fields, it is possible to insert states from h-BN into the bandgap, which generate a conduction channel through the substrate making the system metallic. In addition, we verify that the breakdown voltage strongly depends on the number of h-BN layers. We also show that both the breakdown voltage and the bandgap tuning are independent of the h-BN stacking order. 相似文献
We define the Virasoro algebra action on imaginary Verma modules for affine ${\mathfrak{sl}(2)}$ and construct an analogue of the Knizhnik?CZamolodchikov equation in the operator form. Both these results are based on a realization of imaginary Verma modules in terms of sums of partial differential operators. 相似文献
A random billiard is a random dynamical system similar to an ordinary billiard system except that the standard specular reflection law is replaced with a more general stochastic operator specifying the post-collision distribution of velocities for any given pre-collision velocity. We consider such collision operators for certain random billiards that we call billiards with microstructure. Collisions modeled by these operators can still be thought of as elastic and time reversible. The operators are canonically determined by a second (deterministic) billiard system that models “microscopic roughness” on the billiard table boundary. Our main purpose here is to develop some general tools for the analysis of the collision operator of such random billiards. Among the main results, we give geometric conditions for these operators to be Hilbert-Schmidt and relate their spectrum and speed of convergence to stationary Markov chains with geometric features of the microscopic billiard structure. The relationship between spectral gap and the shape of the microstructure is illustrated with several simple examples. 相似文献
We demonstrate the potential application of silver-pectin nanoparticles on photodynamic therapy, on a solution-base platform. Photodynamic therapy is a medical technique which uses a combination of photosensitizing drugs and light to induce selective damage on the target tissue, by electronically excited and highly reactive singlet state of oxygen. Metal enhanced singlet oxygen generation in riboflavin water solution with silver-pectin nanoparticles was observed and quantified. Here 13 nm silver nanospheres enclosed by a pectin layer were synthesized and it interaction with riboflavin molecule was analyzed. Pectin, a complex carbohydrate found in plants primary cell walls, was used to increase the biocompatibility of the silver nanoparticles and to improve metal enhanced singlet oxygen generation (28.5 %) and metal-enhanced fluorescence (30.7 %) processes at room temperature. The singlet oxygen sensor fluorescent green reagent was used to quantify the enhancement of the riboflavin singlet oxygen production induced by the silver colloid. We report a 1.7-fold increase of riboflavin emission and a 1.8-fold enhancement of singlet oxygen production. 相似文献