全文获取类型
收费全文 | 511篇 |
免费 | 8篇 |
国内免费 | 1篇 |
专业分类
化学 | 367篇 |
晶体学 | 8篇 |
力学 | 21篇 |
数学 | 24篇 |
物理学 | 100篇 |
出版年
2022年 | 13篇 |
2021年 | 10篇 |
2020年 | 4篇 |
2019年 | 11篇 |
2018年 | 2篇 |
2017年 | 8篇 |
2016年 | 7篇 |
2015年 | 5篇 |
2014年 | 16篇 |
2013年 | 43篇 |
2012年 | 29篇 |
2011年 | 34篇 |
2010年 | 16篇 |
2009年 | 25篇 |
2008年 | 19篇 |
2007年 | 30篇 |
2006年 | 16篇 |
2005年 | 25篇 |
2004年 | 19篇 |
2003年 | 24篇 |
2002年 | 23篇 |
2001年 | 9篇 |
2000年 | 6篇 |
1999年 | 10篇 |
1998年 | 6篇 |
1997年 | 2篇 |
1996年 | 4篇 |
1995年 | 10篇 |
1994年 | 7篇 |
1993年 | 7篇 |
1992年 | 6篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1988年 | 8篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 6篇 |
1984年 | 7篇 |
1983年 | 6篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1979年 | 7篇 |
1978年 | 7篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1969年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
1965年 | 1篇 |
排序方式: 共有520条查询结果,搜索用时 15 毫秒
1.
The occurrence of two noninteracting forms of Pd-porphin in the ground electronic state in a wide number of Shpolskii matrices maintained at liquid helium temperature was observed with the help of the finestructure phosphorescence spectra of these systems. The ratio between these forms can be varied in wide limits by choosing a particular matrix, which indicates that the matrix plays a significant role in the conformation formation of the tetrapyrrole macrocycle. Based on comparison both with the resonance Raman spectra and with the results of investigations of metal complexes of porphin by the selective spectroscopy methods, the shortwavelength spectral form has been shown to correspond to the planar molecular structure, whereas the longwavelength form has been attributed to a nonplanar molecular structure with the distortion of the porphin macrocycle of the saddle type. The results obtained indicate that the methods of fine structure spectroscopy make it possible to efficiently study distorted molecular structures stabilized in solid matrices at low temperatures. 相似文献
2.
Using the methods of time-resolved absorption spectroscopy, we have investigated the features of quenching, by molecular oxygen, of the excited triplet states of water-soluble 5,10,15,20-tetrakis-(4-N-methylpyridyl)-porphyrin (H2TMPyP) and 5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin (H2TSPP) in water–ethanol solutions. It has been revealed that for both compounds the rate constant of quenching of the triplet states increases with increasing viscosity of the medium. Quenching of the excited triplet states of the dissociated (in water) and undissociated (in ethanol) forms of water-soluble porphyrins occurs with a different efficiency, and the rate constant of quenching the triplet states by molecular oxygen k T thereby is higher for the dissociated form. It has been shown by means of mathematical modeling that the experimental results obtained can be described in terms of the change in the rate constants of intracomplex transitions in the porphyrin–oxygen collisional complex at varied solution viscosity and their difference for the dissociated and undissociated forms of water-soluble porphyrin. 相似文献
3.
B. M. Dzhagarov N. N. Kruk N. V. Konovalova A. A. Solodunov I. I. Stepuro 《Journal of Applied Spectroscopy》1995,62(2):285-289
Presented at the XV IUPAC Symposium on Photochemistry, Prague, July 17–22, 1994. 相似文献
4.
Orotic acid (vitamin B13) is a key intermediate in biosynthesis of the pyrimidine nucleotides in living organisms, moreover, it may serve as the biological carrier for some metal ions. cis-Diammine(orotato)platinum(II), cis-[Pt(C5H2N2O4)(NH3)2] can be considered as a new potential cisplatin analogue. The FT-Raman and FT-IR spectra of the title complex are reported, for the first time. The molecular structure, vibrational frequencies, and the theoretical infrared and Raman intensities have been calculated by the density functional mPW1PW91 method. The detailed vibrational assignment has been made on the basis of the calculated potential energy distribution. The theoretically predicted IR and Raman spectra show very good agreement with experiment. Natural bond orbital (NBO) analyses were performed for cisplatin, carboplatin and the title complex. The results provided new data on the nature of platinum–ligand bonding in these compounds. Strong intramolecular hydrogen bond between the orotate ligand and the coordinated ammonia group stabilizes the structure of the platinum(II) complex. Thus, it is suggested that the orotate ligand in the title complex is more inert to the substitution reactions than the chloride ligands in cisplatin. 相似文献
5.
A new, high performance liquid chromatography method has been developed for the separation of monovinyl- and divinyl-protochlorophyllides, using commercially available, C30 reverse phase column and isocratic elution. This method can be used both for analytical applications and preparative scale purification of monovinyl- and divinyl-protochlorophyllides using the same column where submilimolar concentrations of the crude protochlorophyllide extract can be separated in one run. The purity of the obtained protochlorophyllides was demonstrated by spectroscopic methods, as well by the formation of aggregates in toluene. 相似文献
6.
JPC – Journal of Planar Chromatography – Modern TLC - Emodin and twelve phenolic acids (ellagic, gallic, protocatechuic, homoprotocatechuic, caffeic, p-hydroxybenzoic, p-coumaric,... 相似文献
7.
We have studied the temperature dependence of the radiative deactivation of the Pd-porphine triplet states in Shpol’skii matrices
in the temperature range 1.2–210 K. A substantial transformation of the phosphorescence spectra is observed as the temperature
increases and is due to the inclusion of thermally activated Pd-porphine states in the radiative deactivation processes. The
activation energy Ea of these Pd-porphine states is measured in matrices of n-octane and n-nonane. The splitting of the lowest quasidegenerate
triplet state ΔE(T2−T1) is determined for planar and distorted conformations of the Pd-porphine macrocycle in the n-octane matrix as 40 and 57 cm−1, respectively. The ability to use the temperature dependence of the phosphorescence properties of Pd-porphine to fabricate
molecular thermometers for the low-temperature range is analyzed.
__________
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 460–464, July–August, 2007. 相似文献
8.
Bonner BE Buchanan JA Clement JM Corcoran MD Krishna NM Kruk JW Miettinen HE Moss RM Mutchler GS Nessi-Tedaldi F Nessi M Phillips GC Roberts JB Stevenson PM Tonse SR Birman A Chung SU Etkin A Fernow RC Kirk H Protopopescu SD Willutzki H Hallman T Madansky L Bar-Yam Z Dowd J Kern W King E Mayes BW Pinsky LS 《Physical review D: Particles and fields》1990,41(1):13-16
9.
Bonner BE Buchanan JA Clement JM Corcoran MD Krishna NM Kruk JW Lincoln DW Miettinen HE Mutchler GS Nessi-Tedaldi F Nessi M Phillips GC Roberts JB Stevenson PM Tonse SR White JL Chung SU Etkin A Fernow RC Protopopescu SD Willutzki H Hallman T Madansky L Pinsky LS 《Physical review letters》1989,62(14):1591-1594
10.
Paramagnetic enhancement of nuclear spin-lattice relaxation rates (PREs) was measured in aqueous solution of the trisaccharide raffinose in the presence of a gadolinium(III) complex, GdDTPA-BMA, used as a magnetic resonance imaging contrast agent. The relaxation enhancement of aqueous protons was measured over a broad range of magnetic fields, using field-cycling apparatus in addition to conventional spectrometers. The nuclear magnetic relaxation dispersion profile thus obtained was interpreted with a recently developed model, allowing for both inner- and outer-sphere relaxation. The relaxation enhancement for the carbon-13 nuclei in raffinose was studied under high-resolution conditions at three magnetic fields, whereas the sugar proton PRE was measured at two fields. The PRE of the sugar nuclei could be interpreted in a consistent way, assuming that it was caused by the outer-sphere mechanism. The electron spin relaxation was found to be a less important source of modulation of the electron-nuclear dipole-dipole interaction than the mutual translational diffusion. 相似文献