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11.
Fiedler SL Vaskonen KJ Eloranta JM Kunttu HM 《The journal of physical chemistry. A》2005,109(20):4512-4516
Electronic spectroscopy of the C(2) molecule is investigated in Ar, Kr, and Xe matrixes in the 150-500 nm range. In the Ar matrix, the D ((1)Sigma(u)(+)) <-- ((1)Sigma(g)(+)) Mulliken band near 240 nm is the sole absorption in the UV range, whereas in the Kr matrix additional bands in the 188-209 nm range are assigned to the Kr(n)()(+)C(2)(-) <-- Kr(n)()C(2) charge-transfer absorptions. Because of the formation of a bound C(2)Xe species, the spectral observations in the Xe matrix differ dramatically from the lighter rare gases: the Mulliken band is absent and new bands appear near 300 and 423 nm. The latter is assigned to the forbidden B'((1)Sigma(g)(+)) <-- X ((1)Sigma(g)(+)) transition, but the origin of the former remains unclear. The spectral assignments are aided by electronic structure calculations at the MCSCF, CCSD(T), and BCCD(T) levels of theory and correlation consistent basis sets. A significant presence of multireference character of the C(2)Xe system was noted and a linear ground-state structure is predicted. The computational results contradict previous density functional studies on the same system. 相似文献
12.
Paavo?Mansikkam?ki Manu?Lahtinen Kari?RissanenEmail author 《Cellulose (London, England)》2005,12(3):233-242
The completeness of mercerisation can be evaluated by investigating the changes in the crystalline regions of cellulose from
cellulose I (C-I) to cellulose II (C-II) by the X-ray powder diffraction method. Mercerisation experiments in four different
solution systems: ethanol/water, acetone, DMSO and xylene, are reported. Also the effect of some additives, external pressure,
treatment time and alkalisation temperature were studied. In two-phase solvent systems, structural changes of cellulose crystallites
depended primarily on the distribution and solubility of sodium hydroxide in the solvent phases. The sodium hydroxide concentration
in the hydrophilic phase must exceed 7–8 w/w-% before complete crystal change from C-I to C-II can occur. The precipitation
of sodium hydroxide due to high concentration prevents the successful use of one-phase ethanol/water system in slurry process.
On the contrary, the 2-propanol/water/sodium hydroxide system separates into two layers; to the water-rich lower layer and
the 2-propanol-rich upper layer, where the sodium hydroxide remains mainly in the water-rich lower layer. This prevents the
precipitation of sodium hydroxide and promotes the alkalisation of cellulose. Ammonium chloride and ammonium hydroxide clearly
had a positive effect by promoting the crystal changes, however, the urea concentration used in this study was obviously too
small. In the advantageous two-phase 2-propanol/water systems, the alkalisation time was only 15 min when the treatment temperature
was kept between 0 and 10 °C. Reduced external pressure was found to have a small but still detectable positive effect on
cellulose alkalisation while over-pressure prevented crystal changes. 相似文献
13.
The suitability of a new technology single-monochromator diode array spectroradiometer for UV-radiation safety measurements, in particular for sunbed measurements, was evaluated. The linearity, cosine response, temperature response, wavelength scale, stray-light and slit function of the spectroradiometer were determined and their effects on the measurement accuracy evaluated. The main error sources were stray-light and nonideal cosine response, for which correction methods are presented. Without correction, the stray-light may reduce the accuracy of the measurement excessively, particularly in the UV-B range. The expanded uncertainty of the corrected UV measurements is estimated to be 14%, which is confirmed with the comparative measurements carried out with a well-characterized double-monochromator spectroradiometer. The measurement accuracy is sufficient for sunbed measurements, provided that all corrections described above have been done and the user of the instrument has a good understanding of the instrument's operating principles and potential error sources. If these requirements are met, the tested spectroradiometer improves and facilitates market surveillance field measurements of sunbeds. 相似文献
14.
Kari Katajamäki 《Results in Mathematics》1996,29(3-4):249-253
Given an algebroid function w satisfying $$w^\nu+A_{\nu-1}(z)w^{\nu-1}+\cdot\cdot\cdot+A_0(z)=0,$$ we establish two general methods to calculate the corresponding coefficients in the defining equation for w′ in terms of the meromorphic functions A0, …, Aν?1 and their derivatives. We then obtain the following result: Let w be a 2-valued algebroid function. Then T(r,w′) = o(T(r,w)) can hold at most on a set of zero upper logarithmic density. 相似文献
15.
Cametti M Nissinen M Dalla Cort A Mandolini L Rissanen K 《Chemical communications (Cambridge, England)》2003,(19):2420-2421
Uranyl-salophen complexes endowed with aromatic side arms behave as very efficient ditopic receptors towards tetralkylammonium halides as a result of a combination of Lewis acid-base and cation-pi interactions. 相似文献
16.
Neuvonen H Neuvonen K Koch A Kleinpeter E 《The journal of physical chemistry. A》2005,109(28):6279-6289
Equilibria between the Z (tau1= 0 degrees) and E (tau1= 180 degrees) conformers of p-substituted phenyl acetates 4 and trifluoroacetates 5 (X = OMe, Me, H, Cl, CN, NO2) were studied by ab initio calculations at the HF/6-31G* and MP2/6-31G* levels of theory. The preference for the Z conformer, DeltaE(HF), was calculated to be 5.36 kcal mol(-1) and 7.50 kcal mol(-1) for phenyl acetate and phenyl trifluoroacetate (i.e., with X = H), respectively. The increasing electron-withdrawing ability of the phenyl substituent X increases the preference of the Z conformer. An excellent correlation with a negative slope was observed for both series between DeltaE of the E-Z equilibrium and the Hammett sigma constant. By using an appropriate isodesmic reaction, it was shown that electron-withdrawing substituents decrease the stability of both conformers, but the effect is higher with the E conformer. Electron-withdrawing phenyl substituents decrease the delocalization of the lone pair of the ether oxygen to the C=O antibonding orbital (nO--> pi*C=O) in both the E and Z forms and in both series studied; this effect is higher in the E conformer than in the Z conformer. The nO --> pi*C=O electron donation has a minimum value with tau1= 90 degrees and a maximum value with tau1= 0 degrees (the Z conformer), the value with tau1= 180 degrees (the E conformer) being between these two values, obviously due to steric hindrance. The effects of the phenyl substituents on the reactivity of the esters studied are discussed in terms of molecular orbital interactions. ED/EW substituents adjust the availability of the pi*C=O antibonding orbital to interact with the lone pair orbital of the attacking nucleophile and therefore affect the reactivity: EW substituents increase and ED substituents decrease it. Excellent correlations were observed between the rate coefficients of nucleophilic acyl substitutions and pi*C=O occupancies of the ester series 4 and 5. 相似文献
17.
Carbonyl carbon (13)C NMR chemical shifts delta(C)(C[double bond]O) measured in this work for a wide set of substituted phenyl benzoates p-Y-C(6)H(4)CO(2)C(6)H(4)-p-X (X = NO(2), CN, Cl, Br, H, Me, or MeO; Y = NO(2), Cl, H, Me, MeO, or NMe(2) ) have been used as a tool to study substituent effects on the carbonyl unit. The goal of the work was to study the cross-interaction between X and Y in that respect. Both the phenyl substituents X and the benzoyl substituents Y have a reverse effect on delta(C)(C[double bond]O). Electron-withdrawing substituents cause shielding while electron-donating ones have an opposite influence, with both inductive and resonance effects being significant. The presence of cross-interaction between X and Y could be clearly verified. Electronic effects of the remote aromatic ring substituents systematically modify the sensitivity of the C[double bond]O group to the electronic effects of the phenyl or benzoyl ring substituents. Electron-withdrawing substituents in one ring decrease the sensitivity of delta(C)(C[double bond]O) to the substitution of another ring, while electron-donating substituents inversely affect the sensitivity. It is suggested that the results can be explained by substituent-sensitive balance of the contributions of different resonance structures (electron delocalization, Scheme 1). 相似文献
18.
Mäkinen M Vainiotalo P Nissinen M Rissanen K 《Journal of the American Society for Mass Spectrometry》2003,14(2):143-151
The ammonium ion binding affinities of tetraethyl resorcarene (1) and its per-methylated derivative (2) were studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. Ten different ammonium ions were tested as guests for the resorcarenes. A strong tendency for complex formation was observed with all ammonium ions of size and charge distribution suitable for noncovalent interactions with the cavities of the resorcarene hosts 1 and 2. Although differences in ammonium ion affinities were observed between 1 and 2 due to the dissimilar conformations, the overall tendency was that increase in the degree of substitution and the length of carbon chain of the ammonium cation facilitated the complex formation until the sterical hindrance impeded the complexation. Dimeric as well as monomeric ammonium ion complexes were formed with resorcarene 1, but resorcarene 2 was unable to form the dimeric capsules because of the lack of H-bond donor possibilities. The nature of binding of the guest was further investigated with ion-molecule reactions and by determination of the single crystal X-ray structure of host 1 complexed with tetramethyl ammonium bromide. 相似文献
19.
Saukkoriipi J Sillanpää A Laasonen K 《Physical chemistry chemical physics : PCCP》2005,7(22):3785-3792
Cationic aluminium(chloro) hydroxide complexes with two to four aluminium atoms were studied using quantum chemical methods. Complexes were studied in both gas and liquid phase. The liquid environment was modeled by using a conductor-like screening model (COSMO). COSMO calculations were carried out as a single point calculation at the optimized gas phase structures. Water (epsilon = 78.54) was used as the solvent. The minimum energy structures obtained from the gas phase studies were mostly compact cyclic structures. Aluminium preferred to be five-coordinated in oxygen rich clusters. Core oxygen preferred three-fold coordination but in the largest clusters the four-coordinated oxygen was observed. Water reacted dissociatively with hydrogen poor clusters. The COSMO calculations showed that the optimal structures of cationic aluminium(chloro) hydroxides tend to be more open in the liquid than in the gas phase. 相似文献
20.
Sara Busi Jarmo Ropponen Jussi Valkonen Kari Rissanen 《Journal of solid state chemistry》2004,177(10):3757-3767
Series of new aromatic R2R′2N+Br− (R=benzyl, 4-methylbenzyl, 2-phenylethyl, 3-phenylpropyl; R′=ethyl, methyl, isopropyl) or RR′2NH+Br−-type (R=benzyl, R′=isopropyl) quaternary ammonium bromides were prepared by using novel synthetic route in which a formamide (N,N-diethylformamide, N,N-dimethylformamide, N,N-diisopropylformamide) is treated with aralkyl halide in presence of a weak base. The compounds were characterized by 1H-NMR and 13C-NMR spectroscopy and mass spectrometry. Structures of the crystalline compounds were determined by X-ray single crystal diffraction, and in addition the powder diffraction method was used to study the structural similarities between the single crystal and microcrystalline bulk material. Three of the compounds crystallized in monoclinic, two in orthorhombic and one in triclinic crystal system, showing ion pairs, which are interconnected by weak hydrogen bonds and weak π-π interactions between the phenyl rings. Three of the compounds appeared as viscous oil or waxes. Finally, TG/DTA and DSC methods were used to analyze thermal properties of the prepared compounds. The lowest melting points were obtained for diethyldi-(2-phenylethyl)ammonium bromide (122.2 °C) and for diethyldi-(3-phenylpropyl)-ammonium bromide (109.1 °C). In general, decomposition of the compounds started at 170-190 °C without identifiable cleavages, thus liquid ranges of 30-70 °C were observed for some of the compounds. 相似文献