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101.
Lamouroux C Aychet N Lelièvre A Jankowski CK Moulin C 《Rapid communications in mass spectrometry : RCM》2004,18(13):1493-1503
The extraction of 135Cs from high-activity liquid waste, arising from reprocessing of spent nuclear fuel, can be achieved by using calix[4]arene crown-6 compounds. The radiolytic degradation of di(n-octyloxy)calix[4]arene crown-6 (octMC6), in aliphatic or aromatic solvent in contact with 3 M nitric acid, was studied by high-performance liquid chromatography directly coupled to electrospray ionisation mass spectrometry (LC/ESI-MS). More than 50 distinct degradation products were observed, and about 30 of these were identified. These compounds can be assigned to three categories, namely, products of reactions involving radical cleavage or addition, of oxidation reactions, or of aromatic substitution reactions. The major product, corresponding to substitution by an NO2 group, was quantified by external standard calibration using a purified synthetic sample. Despite the observation of all these degradation compounds, octMC6 appears to be remarkably stable under these drastic conditions, combining hydrolysis (HNO(3) 3 M) and an extreme exposure to radiolysis (10(6) Gy). Less than 35% degradation of octMC6 was observed in aromatic solvent under these conditions. 相似文献
102.
Maroun RG Zargarian L Stocklin R Troalen F Jankowski CK Fermandjian S 《Rapid communications in mass spectrometry : RCM》2005,19(18):2539-2548
The HIV-1 integrase (IN) catalyzes the integration of viral DNA in the human genome. In vitro the enzyme displays an equilibrium of monomers, dimers, tetramers and larger oligomers. However, its functional oligomeric form in vivo is not known. We report a study of the auto-associative properties of three peptides denoted K156, E156 and E159. These derive from the alpha4 helix of the IN catalytic core. The alpha4 helix is an amphipatic helix exposed at the surface of the protein and could be involved in the oligomerization process through its hydrophobic face. The peptides were obtained from the replacement of several amino acid residues by more helicogenic ones in the alpha4 helix peptide. K156 carries the basic residues Lys156 and Lys159, which have been shown important for the binding of IN to viral DNA. In E156 and E159 they are replaced with the acidic residue Glu. A fourth peptide K(E)156 obtained from the replacement of hydrophobic residues with Glu in K156 in order to abolish the auto-associative properties is used as a negative control. The capacity shown by peptides for alpha-helical formation is demonstrated by circular dichroism (CD) analysis performed in aqueous solution and in aqueous trifluoroethanol (TFE) mixtures. Both electrospray ionization mass spectrometry (ESI-MS) and glutaraldehyde chemical cross-linking show that peptides adopt different solvent-dependent equilibriums of monomers, dimers, trimers and tetramers. Oligomerization of peptides in aqueous solution is related to their ability to form helical structures. Addition of a small amount of TFE (<10%) stimulates helix stabilization and the interhelical hydrophobic contacts. Higher amounts of TFE alter the hydrophobic contacts and disrupt the oligomeric species. In addition to hydrophobic interactions, the patterns indicate that the biologically important Lys156 and Lys159 residues also participate in helix association. K(E)156 despite its ability to adopt a helical structure is unable to associate into oligomers, demonstrating the importance of hydrophobic contacts for oligomerization. Thus, the designed peptides provide us information on the functional properties of the alpha4 IN that seems to hold a dual role in DNA recognition and protein oligomerization. 相似文献
103.
The Baeyer-Villiger oxidation of 7-phosphanorbornene 7-oxides with sterically demanding substituents on the phosphorus atom (4a-d) by m-chloroperbenzoic acid afforded the title products (5a-d) as a mixture of two regioisomers (A and B). Isomer A, the result of thermodynamic control, was stable, while isomer B, the product of kinetic control, underwent decomposition and/or epoxidation. Single crystal X-ray analysis of P-(2,4,6-triisopropylphenyl) oxaphosphabicyclooctene (5Ac) was not only useful in the evaluation of its structure, but, for the first time in the literature, a low-coordinated arylmetaphosphonate (15c) formed by fragmentation on X-ray irradiation could also be detected. The precursors (5Aa-c) were utilized in the thermoinduced and UV light-mediated fragmentation-related phosphorylations of alcohols. Beside the well-known elimination-addition mechanism via the metaphosphonate intermediate (15), a novel addition-elimination route involving a species with a pentavalent pentacoordinated phosphorus atom (16) was also substantiated. 相似文献
104.
Flores JR Słupski R Jankowski K Malinowski P 《The Journal of chemical physics》2004,121(24):12334-12344
To provide very accurate reference results for the second-order M?ller-Plesset (MP2) energy and its various components for Zn(2+), which plays for 3d-electron systems a similar role as Ne for smaller atoms and molecules, we have performed extensive calculation by two completely different implementations of the MP2 method: the finite element method (FEM) and the variation-perturbation (VP) method. The FEM and VP calculations yield partial wave contributions up to l(max)=45 and 12, respectively. Detailed comparison of all FEM and VP energy components for l(max)=12 has disclosed an extraordinary similarity, which justifies using the present results as benchmarks. The present correlation energies are compared with other works. The dependability of an earlier version of FEM, already applied to very large closed-shell atoms, is confirmed. It has been found that for larger atoms the accuracy of the analytical Hartree-Fock results has an impact on the accuracy of the MP2 energies greater than for smaller atoms. Fields of applications of the present results in studies of various electron correlation effects in 3d-electron atoms and molecules are indicated. 相似文献
105.
Steven Ray Wilson Mikolai Jankowski Milaim Pepaj Albena Mihailova Fernando Boix Gabriel Vivo Truyols Elsa Lundanes Tyge Greibrokk 《Chromatographia》2007,66(7-8):469-474
A 2D liquid chromatography (LC) system using hydrophilic interaction chromatography (HILIC) and reversed phase columns has
been employed for comprehensive (LC × LC) separation of rat muscle tissue micro-dialysate. Incorporation of an on-line reverse-phase
solid phase extraction (SPE) enrichment column in front of the first dimension enabled aqueous samples with high salt concentrations
to be injected directly without compromising the chromatographic performance of the HILIC column. Since the SPE enrichment
column allowed injection of large sample volumes (e.g. 450 μL), a capillary HILIC column (inner diameter 0.3 mm) could be
employed instead of a larger column which is often used in the first dimension to load sufficient amounts of sample. The two
chromatographic dimensions were connected using a column selector system with 18, 1.0 mm I.D. C18 “transition” SPE columns. A PLRP C18 column was used in the second dimension. The 2D LC system’s performance was evaluated with a tryptic digest mixture of three
model proteins. Good trapping accuracy (HILIC→transition SPE→RP recovery >95%) and repeatability (within-and between day retention
time RSDs of first and second dimension chromatography >1%) was achieved. A dialysis sample of rat muscle tissue was separated
with the 2D system, revealing complexity and large differences in concentrations of the various compounds present, factors
which could potentially interfere with the quantification and monitoring of two target analytes, arg-bradykinin and bradykinin.
Subsequently, “Heart-cut” 2D LC-electrospray–mass spectrometry (ESI–MS) with post-column on-line standard injection was employed
to monitor arg-bradykinin and bradykinin levels as a function of various muscle conditions. The method’s quantification precision
was RSD = 3.4% for bradykinin. 相似文献
106.
Jankowski P 《The Journal of chemical physics》2008,128(15):154311
Several features and the performance of the recently published [P. Jankowski and M. Ziolkowski, Mol. Phys. 104, 2293 (2006)] three-dimensional intermolecular potential energy surface for the Ar-HF complex have been investigated. This full-dimensional surface has been obtained using the method of the local expansion of the exact interaction energy surface [P. Jankowski, J. Chem. Phys. 121, 1655 (2004)] in the Taylor series with respect to intramolecular coordinates. The interaction energies have been calculated with the coupled-cluster supermolecular method with single, double, and noniterative triple excitations. The convergence of the interaction energy with respect to the size of the basis set is discussed. The two-dimensional surfaces resulting from averaging of the full-dimensional surface over the intramolecular vibration of HF have been obtained and directly compared to the empirical H6(4,3,2) set of surfaces proposed by Hutson [J. Chem. Phys. 96, 6752 (1992)]. A very good agreement has been observed. The averaged potentials have been used to calculate the rovibrational energy levels of the Ar-HF and Ar-DF complexes and compared to the experimental data. The accuracy of rovibrational calculations achieved with the new surface is much better than with any of the ab initio surfaces available so far. Predictions of the rovibrational energy levels and spectroscopic constants have also been done for Ar-HF with HF in the v=4,5 vibrational states, and for Ar-DF and DF in the v=3,4 states. The full-dimensional surface studied in this paper is the first ab initio surface which is fully compatible with the empirical H6(4,3,2) surface proposed by Hutson. 相似文献
107.
Oxidation of chiral Schiff bases lead to nonracemic diasterometric oxaziridines with a preferential formation of an isomer. 相似文献
108.
Thron JL Allison WW Alner GJ Ambats I Ayres DS Balka LJ Barr GD Barrett WL Benjamin D Border PM Brooks CB Cobb JH Cockerill DJ Courant H Dawson JW Demuth DM Edwards VW Ewen B Fields TH Garcia-Garcia C Giles RH Giller GL Goodman MC Gray RN Heilig SJ Hill N Hoftiezer JH Jankowski DJ Johns K Kafka T Kasahara SM Kochocki J Leeson W Litchfield PJ Longley NP Lopez FV Lowe MJ Mann WA Marshak ML May EN Maxam D McMaster L Milburn RH Miller WH Minor CP Napier A Oliver WP Pearce GF Perkins DH Peterson EA 《Physical review D: Particles and fields》1992,46(11):4846-4851
109.
110.