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61.
[reaction: see text] An expedient solid-phase synthetic approach to secondary and tertiary amines was developed. The protocol employs conversion of resin-bound amino alcohols to the corresponding iodides, followed by iodide displacement with primary or secondary amines or with unprotected amino alcohols. This two-step procedure, affording products in good to excellent yields, is suitable for solid-phase synthesis of polyamines. 相似文献
62.
Dyguda E Grembecka J Sokalski WA Leszczyński J 《Journal of the American Chemical Society》2005,127(6):1658-1659
Interaction energies of phenylalanine ammonia-lyase (PAL) active site residues with a series of PAL inhibitors have been partitioned into electrostatic, exchange, delocalization, and correlation components and compared with analogous results obtained previously for leucine aminopeptidase (LAP). In the latter metalloenzyme, either of the two charged residues controls entirely relative inhibitor binding energies, while at least four residues are required to determine ligand relative stabilization in neutral PAL. Significant correlation with experimental inhibitory activity was found between the stabilization energy at gradually decreasing levels of theory (MP2, SCF) down to the first-order Heitler-London term. Contrary to the LAP case, where the electrostatic term was sufficient to reproduce experimentally observed trends, in the case of PAL, exchange repulsion effects also have to be considered. Computational protocol presented herein constitutes a promising way to incorporate the first principle calculation's accuracy into the process of rational binding affinity prediction, revealing the physical nature of the interactions, where successive approximations can be introduced in a systematic and justifiable manner. 相似文献
63.
Jerzy Mroziński Jiří Kohout Mária Hvastijová Helmut Köhler 《Transition Metal Chemistry》1986,11(12):481-484
Summary New coligand isomers of composition Cu{N(CN)2}2(pz)2 and Cu{pz · N(CN)2}2 (pz = pyrazole) were prepared and studied by measuring their magnetic susceptibilities up to 4.2K and by aid of their e.s.r., ligand field and i.r. spectra. The susceptibility data have been analysed with various models for the exchange-coupled copper(II) polymers. It is shown that the resultant exchange coupling is ferromagnetic for Cu{N(CN)2}2(pz)2 (J 1.1 - 1.4 cm–1) but antiferromagnetic for Cu{pz · N(CN)2}2 (J –0.4 cm–1). A polymeric chain structure is proposed for Cu{N(CN)2}2(pz)2 havingpseudo-octahedrally coordinated copper(II) and CN-bridging dicyanamide ligands. Its coligand isomer contains anionic chelate ligands, formed by nucleophilic addition between N(CN)2 and pz in the copper(II) coordination sphere, and giving with this central atom a square-planar system. Definite, but slight axial interaction takes place between these structure units. 相似文献
64.
A method for direct de termination of total in organic arsenic (III+V), arsenic (III) and dimethylarsinate (DMA) in sea water was developed by combining continuous‐flow selective hydride generation and inductively coupled plasma mass spectrometry (ICP‐MS) is presented. The principle underlying selective hydride generation is based on proper control of the reaction conditions for achieving separation of the respective arsenic species. The effects of pH and composition of reaction media on mutual interference between the arsenic species were investigated in detail. The results indicate that the appropriate media for the selective determination of total in organic arsenic, DMA and As(III) are 6 M HNO3, acetate buffer at pH = 4.63 and citrate buffer at pH = 6.54, respectively. The concentrations of total inorganic arsenic species, As(III+V), and As(III) were respectively deter mined and that of As(V) was obtained by the difference between them. As to the concentration of DMA, it was obtained after correction from the interference caused by As(III) and As(V). By following the established procedure, the detection lim its (as based on 3‐sigma criterion) for As(III+V), As(III) and DMA were 0.050, 0.009, and 0.002 ng/mL, respectively. There liability of the pro posed method was evaluated in terms of precision and spike addition. The results indicated that the precision of better than 3% and spike recovery of 95 to 105% for all the arsenic species tested in the natural sea water samples can be obtained. 相似文献
65.
Lapinski L Nowak MJ Kwiatkowski JS Leszczynski J 《Photochemistry and photobiology》2003,77(3):243-252
N2-hydroxyisocytosine and 1-methyl-N2-hydroxyisocytosine were studied using a matrix isolation technique combined with infrared absorption spectroscopy. For N2-hydroxyisocytosine isolated in an Ar matrix (at 10 K), two imino-oxo isomers, one with the hydroxyimino =N-OH group directed toward the N1-H group (the form called further anti) and the second with the =N-OH group directed toward N3-H (syn), were observed in the ratio 1.4:1. The syn isomer is converted totally to the anti form after UV (lambda > 295 nm) irradiation of the matrix. A small amount of the N(3)H-hydroxy-amino tautomer of N2-hydroxyisocytosine was also detected in the matrix. This form did not react photochemically. For 1-methyl-N2-hydroxyisocytosine, only the syn form of the imino-oxo tautomer was observed after deposition of the matrix. UV (lambda > 295 nm) irradiation induced a photoreaction converting this isomer into the anti form. After 15% of the starting material had been converted into the product, a photostationary state was achieved, and no further progress of the reaction was observed. Subsequent UV irradiation (lambda > 335 nm) caused a back reaction, leading to a disappearance of the anti form and to the recovery of the initial syn isomer. All isomers were identified by comparing their experimental IR spectra with the spectra theoretically calculated at the DFT(B3LYP)/6-31G(d,p) level, where DFT is the density functional theory. Good agreement between the observed and predicted patterns of the spectral lines allowed for reliable identification. The experimental IR spectra were interpreted and discussed. The relative energies of the 12 isomers of N2-hydroxyisocytosine were calculated at the MP2/6-31G(d,p) and MP4//MP2/6-31G(d,p) levels. For six isomers of 1-methyl-N2-hydroxyisocytosine, the calculations were carried out at the MP2/6-31G(d,p) level. The anti form of the imino-oxo tautomer of N-hydroxyisocytosine and the syn form of the imino-oxo tautomer of 1-methyl-N2-hydroxyisocytosine were predicted to be the most stable. 相似文献
66.
Katarzyna Guzow Mariusz Szabelski Jerzy Karolczak Wiesaw Wiczk 《Journal of photochemistry and photobiology. A, Chemistry》2005,170(3):215-223
The photophysical properties of N-Boc-3-[2-(9-anthryl)benzoxazol-5-yl]-l-alanine methyl ester (BoxAnt) and N-Boc-3-[2-[4-(9′-(10′-butyl)anthryl)phenyl]benzoxazol-5-yl]-l-alanine methyl ester (BoxPhAnt) were studied in a series of solvents. Their absorption spectra are less sensitive to the solvent polarity than the corresponding fluorescence spectra which show a pronounced solvatochromic effect leading to large Stokes shifts. Using an efficient solvatochromic method, based on the empirical solvent polarity parameter , a large change of the dipole moment on excitation for BoxPhAnt has been found. From an analysis of the solvatochromic behaviour of the absorption and fluorescence spectra in terms of bulk solvent polarity functions, f(r, n) and g(n), a larger excited-state dipole moment (about 8 D, ψ = 56) was obtained for BoxPhAnt than for BoxAnt (about 3 D, ψ = 0). Both applied methods gave similar values of the excited-state dipole moments for both compounds studied. 相似文献
67.
Discrete difference equations in Minkowski space are obtained and the discrete Minkowski force is shown to be a four-vector. A transformation from a discrete dynamical equation in Minkowski space to a Lorentz-invariant difference equation in one-dimensional space is given. 相似文献
68.
Levels of138Ce and140Nd have been studied using the138Ba(α,4nγ)138Ce and140Ce(α, 4nγ)140Nd reactions. Singleγ-ray spectra,γ-γ coincidence spectra, angular and time distributions with respect to the beam bursts have been measured. A number of higher excited states with excitation energies up to about 5 MeV and with spin value up to 12 are populated in both nuclei. The lower states with spins and parities 7?, 5?, 6? and 10+ can be explained by two-quasiparticle neutron configurations of the types (h 11/2 ?1 ,d 3/2 ?1 ) 7? , (h 11/2 ?1 ,S 1/2 ?1 ) 5?, 6? and (h 11/2 ?2 ) 10+. Several high-spin states observed in138Ce and140Nd can be explained qualitatively as four-quasiparticle states with two-proton-two-neutron configurations. The 3? state at an energy of 2,137.4 keV is observed in138Ce. The evidence for the existence of the low-lying 3? states in140Nd at 2,124.0 keV is discussed. Beside the known 9.6 ms (7?) isomeric state in138Ce another state at 3,538.5keV (10+) with a half life of about 200 ns has been observed. The observed levels in the138Ce and140Nd nuclei are compared with theoretical predictions using delta force interaction. 相似文献
69.
Marek Gogacz Jerzy Peszke Dorota Natorska-Chomicka Anna Makuch-Kocka Katarzyna Dos Santos Szewczyk 《Molecules (Basel, Switzerland)》2022,27(23)
Plant extracts are increasingly tested for their biological activity and interactions with neoplastic cells. One of such sources of biologically active substances is propolis. This product has been known for thousands of years and is widely used in alternative, folk medicine. Articles describing its effects on the metabolism and cell signaling pathways of neoplastic cells derived from different organs are also published more and more frequently. The purpose of our study was to evaluate the biological activity of propolis extract produced with the cold separation method into hormone-dependent and hormone-independent prostate cancer cell lines. In our study, the propolis extracts showed at least an inhibitory effect on the growth of PC-3 and DU-145 neoplastic cells. Our results suggest that propolis extracts obtained with the cold separation method may be considered as promising compounds for the production of health-promoting supplements. 相似文献
70.
The formation, properties, decomposition and reactions of ethoxy groups on ZrO2, CuO, and CuO/ZrO2 were followed by IR spectroscopy. The reaction of ethanol with terminal Zr-OH groups leads to the formation of monodendate ethoxy groups (type I), whereas the reaction of ethanol with tribridged Zr-OH grups results in the formation of bidendate ethoxyls (type II). In both cases, water is produced. Ethoxy groups of type II were also formed on CuO. The type of the surface species detected after interaction of ethanol with CuO/ZrO2 was the same as detected for both oxides (i.e., ZrO2 and CuO) separately. This suggests that no new phase was formed in the mixed oxide system. At higher temperatures, ethoxy groups were oxidized forming acetate ions. Gaseous ethanol present in the cell was oxidized to acetaldehyde without the intermediacy of ethoxy groups. 相似文献