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1.
Synthesis of N-and C-substituted derivatives of benzo[h][1,6]naphthyridine, bearing 2-hydroxyethyl group has been made by quaternization reaction and by condensation of corresponding methylbenzonaphthyridines with formaldehyde. For six derivatives of isomeric benzo[c][1,5]-, benzo[h][1,6]-, and benzo[f][1,7]naphthyridines the 13C NMR spectra are discussed. For ten compounds the geometry was optimized with the AM1 and, in one case also with the ab initio 6–31G method; their effective charge values have also been calculated.  相似文献   
2.
A new formula for the nuclear charge radius is proposed, dependent on the mass numberA and neutron excessN-Z in the nucleus. It is simple and it reproduces all the experimentally available mean square radii and their isotopic shifts of even-even nuclei much better than other frequently used relations.This work is partly supported by the Polish Committee of Scientific Research under contract No. 203119101  相似文献   
3.
A symmetry-adapted perturbation theory based on Kohn-Sham determinants [SAPT(KS)] and utilizing asymptotically corrected exchange-correlation potentials has been applied to the He2, Ne2, (H2O)2, and (CO2)2 dimers. It is shown that SAPT(KS) is able to recover the electrostatic, first-order exchange, second-order induction, and exchange-induction energies with an accuracy approaching and occasionally surpassing that of regular SAPT at the currently programmed theory level. The use of the asymptotic corrections is critical to achieve this accuracy. The SAPT(KS) results can be obtained at a small fraction of the time needed for regular SAPT calculations. The robustness of the SAPT(KS) method with respect to the basis set size is also demonstrated. A theoretical justification for high accuracy of SAPT(KS) predictions for the electrostatic, first-order exchange, and second-order induction energies has been provided.  相似文献   
4.
A two-dimensional (rigid monomer) intermolecular potential energy surface (PES) of the He-HCl complex has been obtained from ab initio calculations utilizing the symmetry-adapted perturbation theory (SAPT) and an spdfg basis set including midbond functions. The bond length in HCl was chosen to be equal to the expectation value in the ground vibrational state of isolated HCl. The rigid-monomer potential should be a very good approximation to the complete (three-dimensional) potential for H-Cl distances corresponding to the lowest vibrational levels of the monomer since the He-HCl interaction energy was found to be only weakly dependent on the HCl bond length in this region, at least as compared to systems such as Ar-HF. The calculated points were fitted using an analytic function with ab initio computed asymptotic coefficients. As expected, the complex is loosely bound, with the dispersion energy providing the majority of the attraction. Our SAPT PES agrees with the semiempirical PES of Willey et al. [J. Chem. Phys. 96, 898 (1992)], in finding that, atypically for rare gas-hydrogen halide complexes including the lighter halide atoms, the global minimum is on the Cl side (with intermonomer separation 3.35 A and depth of 32.8 cm(-1)), rather than on the H side, where there is only a local minimum (3.85 A, 30.8 cm(-1)). The ordering of the minima was confirmed by single-point calculations in larger basis sets and complete basis set extrapolations, and also using higher levels of theory. We show that the opposite findings in the recent calculations of Zhang and Shi [J. Mol. Struct: THEOCHEM 589, 89 (2002)] are due to the lack of midbond functions in their basis set. Despite the closeness in depth of the two linear minima, the existence of a relatively high barrier between them invalidates the assumption of isotropy, a feature of some literature potentials. The trends concerning the locations of minima within the family of rare gas-hydrogen halide complexes are rationalized in terms of the physical components of the intermolecular forces and related to monomer properties. The accuracy of the SAPT PES was tested by performing calculations of rovibrational levels. The transition frequencies obtained were found to be in excellent agreement (to within 0.02 cm(-1)) with the measurements of Lovejoy and Nesbitt [J. Chem. Phys. 93, 5387 (1990)]. The SAPT PES predicts a dissociation energy for the complex of 7.74 cm(-1) which is probably more accurate than the experimental value of 10.1+/-1.2 cm(-1). Our analysis of the ground-state rovibrational wave function shows that the He-HCl configuration is favored over the He-ClH configuration despite the ordering of minima. This is due to the greater volume of the well in the former case. We have also determined positions and widths of three low-lying resonance states through scattering calculations. These predictions are expected to be more accurate than values derived from experiment.  相似文献   
5.
The electron impact mass spectra of 6-methyltetrazolo[1,5-c]pyrimidin-5(6H)-one, its 7- and 8-methyl derivatives, three 8-halo derivatives and two related nucleosides are reported. On the basis of the high-resolution data and detected metastable ions, the fragmentation routes of their molecular ions are proposed. Coexistence of the tautomeric forms of the title compounds of cyclic (tetrazole) or linear (azide) structure can be suggested owing to the fragmentation pathways identified for the bases. Decomposition of the related nucleosides lies in the breaking of nucleoside bonds to produce the appropriate base and sugar fragments.  相似文献   
6.
We find a condition (6) under which a gauge theory of the Poincaré group is equivalent to the Einstein-Cartan theory of gravitation.  相似文献   
7.
A one-step solid-phase extraction procedure, based on a new silica gel adsorbent modified with cholesterol groups, has been investigated for measurement of cotinine in urine. Cotinine is the main metabolite of nicotine in the human body and is analyzed as a biomarker for assessment of direct or passive exposure to tobacco smoke. New cholesterol-modified adsorbents have been obtained by chemical modification of silica gel of different porosity with cholesterol ligands. Although recovery by this extraction procedure were optimum over a relatively broad range of sample pH (3.1–8.0), analytical conditions such as sample loading, washing and elution conditions, concentration of cotinine to be extracted, and the type of adsorbent used for extraction were found to affect the efficiency of the procedure and had to be controlled for optimum recovery. When these conditions were controlled, recovery of cotinine from spiked human urine was reproducible and depended on compound ionization. Quantitative analysis of cotinine was performed by reversed-phase high-performance liquid chromatography with UV detection. Presented at: Conference of the Hyphenation of Liquid Chromatography–Nuclear Magnetic Resonance Spectroscopy, Liquid Chromatography–Mass Spectrometry and Related Topics, Tuebingen, Germany, March 25–29, 2006.  相似文献   
8.
Acyclic nucleosides of 4‐nitro‐1H‐imidazole and 4‐nitropyrazole have been synthesized by nucleophilic addition of the appropriate 4‐nitroazole to (?)‐(S)‐(hydroxymethyl)oxirane in the presence of a catalytic amount of potassium carbonate. (+)‐(R)‐3‐(4‐nitro‐1H‐imidazol‐1‐yl)propane‐1,2‐diol and (+)‐(R)‐3‐(2‐methyl‐4‐nitro‐1H‐imidazol‐1‐yl)propane‐1,2‐diol were also obtained in an independent reaction starting from appropriate 1,4‐dinitro‐1H‐imidazole and (+)‐(R)‐3‐aminopropane‐1,2‐diol. (+)‐(R)‐3‐(4‐Nitropyrazol‐1‐yl)propane‐1,2‐diol was also obtained by direct noncatalyzed addition of 4‐nitropyrazole to (?)‐(S)‐(hydroxymethyl)oxirane, whereas the (S)‐enantiomer was obtained by reaction of 4‐nitropyrazole with (+)‐(S)‐1,2‐O‐isopropylideneglycerol under Mitsunobu reaction conditions, followed by a cleavage of the isopropylidene group with 80% AcOH. Racemization during any of these syntheses has not been observed. 3‐(4‐Nitroazol‐1‐yl)propane‐1,2‐diols were incorporated into a 26‐mer oligonucleotide. UV Thermal melting studies of duplexes of the oligonucleotides with 4‐nitropyrazole or 4‐nitro‐1H‐imidazole paired with four natural bases showed moderately decreased stabilities of the duplexes. A narrow range of melting temperatures, typically being within 2° for each acyclic nucleoside, fulfill one of the requirements of using acyclic 4‐nitroazoles as general bases. Single incorporation of 4‐nitroazoles into a 14‐mer triplex forming oligonucleotide resulted in considerably decreased triplex stabilities.  相似文献   
9.
Polymerization of THF in CCl4 solvent was initiated with 1,3-dioxolan-2-ylium eations with AsF6?, PF6?, and SbF6? anions as well as with esters of fluorosulfonic and trifluoromethanesulfonic acids. With these esters polymerization proceeds with a marked acceleration period, due to slow initiation. The corresponding rate constants of initiation and their dependence on the polarity of the THF/CCl4 mixture were determined. The rate constant of propagation on the macroion-pairs (kp±) of the polytetrahydrofurylium cation with AsF6?, PF6?, and SbF6? and CF3SO3?, anions was found to be independent in CCl4 solvent on the anion structure and given by the expression: kp± = 2.93 × 10?2 exp {?4.7 × 103/T} at [THF]0 = 8.0M. This constant depends on the polarity of the polymerization mixture, and at 25°C for the THF-CCl4 system, kp± = 1.78 × 10?2 exp {?4.9/D}; thus, in CCl4 at [THF]0 = 8.0M, and at 25° kp± = 4.0 × 10?21/mole-sec. In the polymerization with derivatives of CF3SO3H (able to form the corresponding macroester) the overall polymerization rate is much lower than that with complex anions because of the reversible conversion of the macroion-pairs into the macroester (internal return). The macroester is much less reactive than the macroionpair (102–103 times) in the monomer addition reaction. At [THF]0 = 8.0M and at 25°C, 96.5% of the growing species exists in the macroester form. Polymerization of THF initiated with derivatives of CF3SO3H is a subject of a strong special salt-effect. At a sufficiently high ratio of [AgSbF6] to [I]0, where the initiator I is C2H5OSO2CF3, the overall polymerization rate is equal to that observed for the polymerization of THF on the macroion-pairs, since the internal return within the triflate ion-pair (the macroester formation) is eliminated and polymerization proceeds on the macroion-pairs with SbF6- anions exclusively.  相似文献   
10.
Small-angle x-ray scattering (SAXS) and scanning electron microscopy (SEM) investigations for epoxidized butadiene-styrene (BS) block copolymers were performed. For unepoxidized copolymers, the SAXS curve exhibits a maximum which indicates that the copolymer has heterogeneity domain morphology. Using the standard theory for a two-phase system, mean distances between domains, the correlation length l p , and the thickness of the phase boundary were calculated from the SAXS data. It was found that the epoxidation of BS copolymers decreases the ability of the copolymer to separate the individual components. As the content of the epoxide groups increases, the dimensions of the domains decrease until they disappear, the boundary between domains and the matrix becomes less and less definite, and the copolymer composes a homogeneous system. The disappearance of the two-phase structure of the BS copolymers indicates an increase in the compatibility of polystyrene and epoxidized polybutadiene. According to the method of Van Krevelen, the solubility parameters of polystyrene and epoxypolybutadiene were calculated. Small differences between these parameters support the conclusions drawn from the SAXS investigations  相似文献   
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