全文获取类型
收费全文 | 3786篇 |
免费 | 50篇 |
国内免费 | 27篇 |
专业分类
化学 | 2592篇 |
晶体学 | 59篇 |
力学 | 113篇 |
数学 | 720篇 |
物理学 | 379篇 |
出版年
2020年 | 28篇 |
2016年 | 41篇 |
2015年 | 36篇 |
2014年 | 42篇 |
2013年 | 166篇 |
2012年 | 128篇 |
2011年 | 139篇 |
2010年 | 81篇 |
2009年 | 74篇 |
2008年 | 146篇 |
2007年 | 149篇 |
2006年 | 176篇 |
2005年 | 164篇 |
2004年 | 132篇 |
2003年 | 144篇 |
2002年 | 108篇 |
2001年 | 52篇 |
2000年 | 52篇 |
1999年 | 42篇 |
1998年 | 30篇 |
1997年 | 57篇 |
1996年 | 59篇 |
1995年 | 60篇 |
1994年 | 61篇 |
1993年 | 66篇 |
1992年 | 44篇 |
1991年 | 66篇 |
1990年 | 51篇 |
1989年 | 48篇 |
1988年 | 45篇 |
1987年 | 38篇 |
1986年 | 40篇 |
1985年 | 72篇 |
1984年 | 78篇 |
1983年 | 50篇 |
1982年 | 80篇 |
1981年 | 73篇 |
1980年 | 65篇 |
1979年 | 78篇 |
1978年 | 70篇 |
1977年 | 73篇 |
1976年 | 60篇 |
1975年 | 56篇 |
1974年 | 69篇 |
1973年 | 80篇 |
1972年 | 39篇 |
1971年 | 39篇 |
1970年 | 35篇 |
1969年 | 28篇 |
1968年 | 30篇 |
排序方式: 共有3863条查询结果,搜索用时 0 毫秒
71.
Krizek DT 《Photochemistry and photobiology》2004,79(4):307-315
The role of photosynthetically active radiation (400-700 nm) (PAR) in modifying plant sensitivity and photomorphogenic responses to ultraviolet-B (280-320 nm) (UV-B) radiation has been examined by a number of investigators, but few studies have been conducted on ultraviolet-A (320-400 nm) (UV-A), UV-B and PAR interactions. High ratios of PAR-UV-B and UV-A-UV-B have been found to be important in ameliorating UV-B damage in both terrestrial and aquatic plants. Growth chamber and greenhouse studies conducted at low PAR, low UV-A and high UV-B often show exaggerated UV-B damage. Spectral balance of PAR, UV-A and UV-B has also been shown to be important in determining plant sensitivity in field studies. In general, one observes a reduction in total biomass and plant height with decreasing PAR and increasing UV-B. The protective effects of high PAR against elevated UV-B may also be indirect, by increasing leaf thickness and the concentration of flavonoids and other phenolic compounds known to be important in UV screening. The quality of PAR is also important, with blue light, together with UV-A radiation, playing a key role in photorepair of DNA lesions. Further studies are needed to determine the interactions of UV-A, UV-B and PAR. 相似文献
72.
The amphiphilic shape-persistent macrocycle 1 containing four phenol-OH groups as polar side groups and four hexyloxy groups as nonpolar side groups in an adaptable arrangement was recrystallized from solvents of different polarity. X-ray crystallography reveals that the conformation of the macrocycle is solvent dependent such that in the pyridine solvate only two of the nonpolar side groups point outward while in the THF solvate all four of them point outward. Moreover, in the latter case the three-dimensional packing leads to the formation of a supramolecular channel structure with a large pore size. 相似文献
73.
Kaster Jeffrey A. Michelsen Donald L. Velander William H. 《Applied biochemistry and biotechnology》1990,(1):469-484
A microbubble dispersion (MBD) was used to supply oxygen for aerobic fermentations in a standard 2 L stirred tank fermenter.
The microbubble dispersion was formed using only surfactants produced naturally. Growth rates ofSaccharomyces cerevisiae cultures were found to be equal or greater with MBD sparging than with gas sparging. The oxygen transfer coefficent with
MBD sparging was found to be 190/h and independent of impeller speed from 100–580 rpm. The oxygen transfer coefficient with
air sparging rose from 55 to 132/h over the same range of impeller speeds. Power requirements for the fermenter systems were
estimated. 相似文献
74.
The performance of an inexpensive, inductive rule-building expert shell system, based on the ID3 algorithm, was compared to that of SIMCA class modeling in classifying the binary mass spectra of 78 toxic and related compounds. The compressed mass spectra consisted of 17 masses chosen by using information theory. The expert rules verified the six main classes and two subclasses found with SIMCA class modeling. These classes were: all benzenes and all alkanes/ alkenes (alka(e)nes); nonhalobenzenes, chlorobenzenes, bromoalka(e)nes, and chloroalka(e)nes; and mono-, dichloroalka(e)nes and polychloroalka(e)nes. Training set classification accuracies obtained with the expert system were 93–100% as opposed to 62–98% for SIMCA. For 73 compounds, the expert rules gave a classification accuracy of 97–100% vs. 79–96% for SIMCA. Predictive accuracy for the four main classes was 78%. In general, fewer masses were involved with the rules than with the SIMCA models, and the rules are normally optimized with regard to minimum number of steps in the rule, not minimum number of variables. The expert rules work best with closed sets of objects where all possibilities can be included in the training sets. The expert rules represent planes partitioning the multidimensional measurement space (hypercube) into a subvolume nearest the SIMCA cylinders for an appropriate class. Overall, the performance of the expert system was very good. 相似文献
75.
Reza Dabesrani Robert H. Sik Donald G. Davis George Dubay Colin F. Chignell 《Photochemistry and photobiology》1993,58(3):367-373
Abstract— The photochemistry, photophysics, and photosensitization (Type I and II) of indomethacin (IN) (N-[p-chlorobenzoyl]-5-methoxy-2-methylindole-3-acetic acid) has been studied in a variety of solvents using NMR, high performance liquid chromatography-mass spectroscopy, transient spectroscopy, electron paramagnetic resonance in conjunction with the spin trapping technique, and the direct detection of singlet molecular oxygen (l O2) luminescence. Photodecomposition of IN (λex > 330 nm) in degassed or air-saturated benzene proceeds rapidly to yield a major (2; N-[p-chlorobenzoyl]-5-methoxy-2-methyl-3-methylene-indoline) and a minor (3; N-[p-chlorobenzoyl]-5-methoxy-2, 3-dimethyl-indole) decarboxylated product and a minor indoline (5; 1-en-5-methoxy-2-methyl-3-methylene-in-doline), which is formed by loss of the p-chlorobenzoyl moiety. In air-saturated solvents two minor oxidized products 4 (N-[p-chlorobenzoyl]-5-methoxy-2-methylindol-3-aldehyde) and 6 (5-methoxy-2-methyl-indole-3-aldehyde) are also formed. When photolysis was carried out in 18O2-saturated benzene, the oxidized products 4 and 6 contained 18O, indicating that oxidation was mediated by dissolved oxygen in the solvent. In more polar solvents such as acetonitrile or ethanol, photodecomposition is extremely slow and inefficient. Phosphorescence of IN at 77 K shows strong solvent dependence and its emission is greatly reduced as polarity of solvent is increased. Flash excitation of IN in degassed ethanol or acetonitrile produces no transients. A weak transient is observed at 375 nm in degassed benzene, which is not quenched by oxygen. Irradiation of IN (λex > 325 nm) in N2-gassed C6H6 in the presence of 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) results in the trapping of two carbon-centered radicals by DMPO. One adduct was identified as DMPO/.COC6H4-p-CI, while the other was probably derived from a radical formed during IN decarboxylation. In air-saturated benzene, (hydro) peroxyl and alkoxyl radical adducts of DMPO are observed. A very weak luminescence signal from 1O2 at 1268 nm is observed initially upon irradiation (λex= 325 nm) of IN in air-saturated benzene or chloroform. The intensity of this 1O2 signal increases as irradiation is continued suggesting that the enhancement in 1O2 yield is due to photoproduct(s). Accordingly, when 2 and 3 were tested directly, 2 was found to be a much better sensitizer of 1O2 than IN. In air-saturated ethanol or acetonitrile no IN 1O2 luminescence is detected even on continuous irradiation. The inability of IN to cause phototoxicity may be related to its photo stability in polar solvents, coupled with the low yield of active oxygen species (1O2, O2?-) upon UV irradiation. 相似文献
76.
Two Novel long chain fatty acids, (5Z, 9Z)-6-bromo-25-methyl-5,9-hexacosadienoic and (5Z, 9Z)-6-bromo-24-methyl-5,9-hexacosadienoic acids were found in the phospholipids of and . Their structures were elucidated with the help of CI-EI7MS and a homogeneous hydrogenation catalyst. 相似文献
77.
Donald G. Fleming Donald J. Arseneau David M. Garner Masayoshi Senba Randall J. Mikula 《Hyperfine Interactions》1984,18(1-4):655-678
The vapor phase fractional polarizations of positive muons thermalizing as the muonium atom (P
M) and in diamagnetic environments (P
D) has been measured in H2O, CH3OH, C6H14, C6H12, CCl4, CHCl3, CH2Cl2 and TMS, in order to compare with the corresponding fractions measured in the condensed phases. There is a marked contrast in every case, with the vapor phase results being largely understandable in terms of a charge exchange/hot atom model. Unlike the situation in the corresponding liquids, there is no permanent lost fraction in the vapor phase in the limit of even moderately high pressures (1 atm); at lower pressures, depolarization is due to hyperfine mixing and is believed to be well understood. For vapor phase CH3OH, C6H14, C6H12, and TMS therelative fractions are found to be pressure dependent, suggesting the importance of termolecular hot atom (or ion) reactions in the slowing down process. For vapor phase H2O and the chloromethanes, the relative fractions are pressure independent. For CCl4,P
M=P
D0.5 in the vapor phase vs.P
D=1.0 in the liquid phase; fast thermal reactions of Mu likely contribute significantly to this difference in the liquid phase. For H2O,P
M 0.9 andP
D0.1 in the vapor phase vs.P
D 0.6 andP
M0.2 in the liquid phase. Water appears to be the one unequivocal case where the basic charge exchange/hot atom model is inappropriate in the condensed phase, suggesting, therefore, that radiation induced spur effects play a major role. 相似文献
78.
An unprotected 16 residue peptide containing a C-terminal thioester and an N-terminal selenocysteine residue efficiently cyclizes in the presence of thiophenol; subsequent reduction, elimination or alkylation of the selenol yields modified cyclic peptides with alanine, dehydroalanine or a non-natural amino acid at the site of ligation. 相似文献
79.
Probabilities of peak occurrence and information content of the NBS/EPA/MSDC mass-spectral data base
The probabilities of peak occurrence and contents of binary information were calculated for the 43 990 mass spectra in the 1987 NBS/EPA/MSDC data base. The median molecular weight of compounds in the data base was 230. Compounds composed of combinations of C, H, N, and O comprised 64% of the data base. The numbers of base peaks per mass channel are tabulated. A subset of compounds (30480) with low molecular weights was selected as a volatile-compound data base; the median molecular weight of this group was 189. The probabilities and information contents for the whole set of spectra and the volatile hydrocarbons, oxygenated hydrocarbons, chlorocarbons and chlorohydrocarbons and bromohydrocarbons were calculated. The most common peak in the entire data base and in the volatile set occurred at mass 41. All peaks in both of these sets of spectra with probabilities greater than 0.50 occurred below mass 78. The probabilities over the total and volatile-compound data base showed a general decrease with increasing mass channel with a division into odd- and even-mass curves which converged at high masses. Mass channels with 0.90–1.0 bit information content occurred below ca. mass 100. Information contents decreased with increasing mass and the two odd- and even-mass curves were superimposed on the general trend. 相似文献
80.
Experimental data on initial hydrate formation conditions have been obtained for the nitrogen-propane-water system in the L1HG, L1L2H, and L1L2HG regions, where L1 is the water rich liquid phase, L2 is the hydrocarbon rich liquid phase, H is the hydrate and the G is the vapor phase. The measurements covered a range of temperatures from about 275 to 293 K and pressures from about 0.3 to 17.0 MPa. The concentrations covered for the L1HG region extended from 0.94 to 75.0 mole percent propane in the gas phase, and for the L1L2H region they extended from 83.1 to 99.0 mole percent in the condensed liquid phase. Four-phase measurements were made at concentrations of propane from 18.1 to 71.1 mole percent in the gas phase.The experimental data were used to find a fitted binary interaction parameter for predicting hydrate formation in systems containing nitrogen and propane. 相似文献