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1.
A theoretical survey of the electronic structure of Ca(2) is presented using two-electron pseudopotentials complemented by core-polarization operators on Ca atoms and multireference configuration interaction/quasidegenerate perturbation theory (MRCI/QDPT) treatment of molecular excited states. The spectroscopic constants of 70 electronic states up to 30,000?cm(-1) above the ground state are determined. This implies all Ca(2) states dissociating up to the Ca(4s(2) (1)S) + Ca(4s5p (3,1)P) dissociation limits. All spin states (singlet, triplet, and quintet) are investigated. The work emphasizes the variety of interactions implying singly valence and lowest Rydberg excited states, doubly excited states generated by atom pairs (3)P(4s4p) + (3)P(4s4p), or (3)P(4s4p) + (3)D(4s3d), 4p3d double excitations asymptotically localized on a single-atom. Zwitterionic Ca(+) + Ca(-) configurations are evidenced and shown to induce specific electronic patterns in (1)Σ(g)(+), (3)Σ(g)(+), (1)Σ(u)(+), (3)Σ(u)(+), (1)Π(g), (3)Π(g), (1)Π(u), and (3)Π(u) symmetry manifolds. They also provide insight for qualitative features (barriers) found for the lower electronic states already investigated in previous publications by other authors. 相似文献
2.
Dillmann B Elbayed K Zeiger H Weingertner MC Piotto M Engelke F 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,187(1):10-18
A novel coil, called Z coil, is presented. Its function is to reduce the strong thermal effects produced by rf heating at high frequencies. The results obtained at 500MHz in a 50 microl sample prove that the Z coil can cope with salt concentrations that are one order of magnitude higher than in traditional solenoidal coils. The evaluation of the rf field is performed by numerical analysis based on first principles and by carrying out rf field measurements. Reduction of rf heating is probed with a DMPC/DHPC membrane prepared in buffers of increasing salt concentrations. The intricate correlation that exists between the magnetic and electric field is presented. It is demonstrated that, in a multiply tuned traditional MAS coil, the rf electric field E(1) cannot be reduced without altering the rf magnetic field. Since the detailed distribution differs when changing the coil geometry, a comparison involving the following three distinct designs is discussed: (1) a regular coil of 5.5 turns, (2) a variable pitch coil with the same number of turns, (3) the new Z coil structure. For each of these coils loaded with samples of different salt concentrations, the nutation fields obtained at a certain power level provide a basis to discuss the impact of the dielectric and conductive losses on the rf efficiency. 相似文献
3.
Bautista-Sanchez A Kasselouri A Desroches MC Blais J Maillard P de Oliveira DM Tedesco AC Prognon P Delaire J 《Journal of photochemistry and photobiology. B, Biology》2005,81(3):154-162
Glucoconjugated analogues of the meta-hydroxyphenyl porphyrin (m-THPP) and meta-hydroxyphenyl chlorin (m-THPC) has been recently synthesized. The characteristics of their triplet states have been determined with regard to their involvement in the photodynamic (PDT) efficiency. In the case of porphyrin derivatives, triplet quantum yields (Phi(T)) were ranging from 0.42 to 0.55 and triplet life times (tau(T)) from 1 to 5 micros. High reaction rate constants (k(q)) with molecular oxygen (k(q): 1.2-1.6 x 10(9)s(-1)) have been found. The triplet lifetimes of chlorin derivatives were about four times higher than those of porphyrins whereas the Phi(T) and k(q) values remained quite similar. Singlet oxygen yields of glucosylated and non-glucosylated porphyrins and chlorins were not significantly different within experimental errors (Phi(Delta)((1)O(2)): 0.41-0.58). Furthermore, it has been shown that glucoconjugated photosensitizers could undergo associations with the methyl-beta-cyclodextrin (Me-beta-CD) which exhibit high triplet lifetimes and singlet oxygen yields ranging from 0.27 to 0.48. 相似文献
4.
Desroches MC Kasselouri A Meyniel M Fontaine P Goldmann M Prognon P Maillard P Rosilio V 《Langmuir : the ACS journal of surfaces and colloids》2004,20(26):11698-11705
The use of porphyrin derivatives in photodynamic therapy is of excellent prospect for the treatment of superficial or easily reachable tumors. The selection of porphyrin derivatives by tumor cells depends to a large extent of their ability to interact with the biological membrane. The evaluation of porphyrin interaction with phospholipids can thus be used as a screening method. In this work we report on the assessment of the interaction of three new porphyrin derivatives with various phospholipids forming Langmuir films by surface tension and surface pressure measurements, grazing incidence X-ray diffraction, and liquid chromatography on an IAM stationary phase. The results show that the hydroxylated phenylporphyrin (m-THPP) is able to interact with all studied phospholipids and to significantly disorganize the structure of their monolayers. Obviously, the interaction occurs at the level of the hydrophobic chains of a phospholipid. A triglucoconjugated phenylporphyrin (m-TPP(Glu)3) also interacts with the phospholipids though to a lesser extent. Conversely, the tetraglucoconjugated derivative (m-TPP(Glu)4) exhibits both a weak surface activity and a poor affinity for the studied phospholipids. Thus, whereas m-THPP and m-TPP(Glu)3 are expected to penetrate into a biological membrane, m-TPP(Glu)4 seems unlikely to do so. 相似文献
5.
Bilal Elhajjar Abdelkader Mojtabi Manuel Marcoux Marie-Catherine Charrier-Mojtabi 《Comptes Rendus Mecanique》2006,334(10):621-627
We propose an analytical and numerical study of the combined action of the thermodiffusion and the convection in a binary mixture. The combination of these two phenomena is called thermogravitational diffusion. We are interested in quantifying the separation in a horizontal parallelepipedic cavity filled with a binary mixture and subjected to a constant horizontal temperature gradient on the two horizontal walls, the other walls being thermally insulated and impermeable. This new procedure is different from the classical one where the cavity is vertical and differentially heated on the two vertical walls. To cite this article: B. Elhajjar et al., C. R. Mecanique 334 (2006). 相似文献
6.
Desroches MC Bautista-Sanchez A Lamotte C Labeque B Auchère D Farinotti R Maillard P Grierson DS Prognon P Kasselouri A 《Journal of photochemistry and photobiology. B, Biology》2006,85(1):56-64
Photodynamic therapy (PDT) involves a non invasive treatment of small and superficial cancers using a photosensitive drug and light to kill tumoral cells. 5,10,15-meso-tri-(meta-O-beta-D-glucosyloxyphenyl)-20-phenylporphyrin [m-TPP(glu)3] is a new photosensitizer (PS) with more enhanced photocytotoxicity relative to 5,10,15,20-meso-tetra-(meta-hydroxyphenyl) chlorin [m-THPC] (Foscan). It was injected intravenously once to healthy rats at three different doses (0.25, 0.5 and 1 mg kg(-1)) and compared to m-THPC (0.3 mg kg(-1)). Pharmacokinetic parameters for both photosensitizers were derived from plasma concentration-time data using a non-compartmental analysis and a two-compartment pharmacokinetic model. m-TPP(glu)3 is more rapidly eliminated throughout the organism than m-THPC. Its mean plasma clearance is 19 mL h(-1) kg(-1) (6 mL h(-1) kg(-1) for m-THPC), and its mean residence time is 5h (20 h for m-THPC). The area under curve (AUC) and initial mean serum concentration (C0) were found to be proportional to the dose. As for Foscan, no metabolite of m-TPP(glu)3 was detected in plasma. The biodistribution study demonstrates that the most significant amount of m-TPP(glu)3 was concentrated in organs such as lung, liver and spleen which are rich in reticulo-endothelial cells. Maximum concentrations were reached in organs 14 h after IV administration. At 48 h, the photosensitizer was essentially eliminated from all organs. Because of its shorter elimination time, m-TPP(glu)3 is more attractive than m-THPC as a PDT agent since secondary side effects of shorter duration could be expected. 相似文献
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8.
Greg Erickson Jiasheng Guo Mike McClure Mark Mitchell Marie-Catherine Salaun Andrew Whitehead 《Tetrahedron letters》2014
A new synthesis of Lapatinib, an orally active drug for breast cancer, is described. The synthesis involves a palladium catalyzed regioselective arylation of furfural with 6-bromo-N-(3-chloro-4-((3-fluorobenzyl)oxy)phenyl)quinazolin-4-amine. This key step replaces an atom inefficient Suzuki cross coupling reaction used in a previously disclosed route and significantly shortens the synthesis. 相似文献
9.
In this paper, we consider the effect of mechanical vibration on the onset of convection in porous media. The porous medium
is saturated either by a pure fluid or by a binary mixture. The importance of a transport model on stability diagrams is presented
and discussed. The stability threshold for the Darcy–Brinkman case in the Ra
Tc
-R and k
c
-R diagrams is presented (where Ra
Tc
, k
c
and R are the critical Rayleigh number, the critical wave number and the vibration parameters, respectively). It is shown that
there is a significant deviation from the Darcy model. In the thermo-solutal case with the Soret effect, the influence of
vibration on the reduction of multi-cellular convection is emphasized. A new analytical relation for obtaining the threshold
of mono-cellular convection is derived. This relation shows how the separation factor Ψ is related to the controlling parameters
of the problem, Ψ = f (R, ε*, Le), when the wave number k → 0. The importance of vibrational parameter definition is highlighted and it is shown how, by using a proper definition
for vibrational parameter, we may obtain compact relationship. It is also shown how this result may be used to increase component
separation. 相似文献
10.