全文获取类型
收费全文 | 26693篇 |
免费 | 4325篇 |
国内免费 | 3859篇 |
专业分类
化学 | 19989篇 |
晶体学 | 324篇 |
力学 | 1681篇 |
综合类 | 341篇 |
数学 | 3299篇 |
物理学 | 9243篇 |
出版年
2024年 | 46篇 |
2023年 | 410篇 |
2022年 | 522篇 |
2021年 | 724篇 |
2020年 | 887篇 |
2019年 | 986篇 |
2018年 | 752篇 |
2017年 | 782篇 |
2016年 | 1112篇 |
2015年 | 1173篇 |
2014年 | 1434篇 |
2013年 | 1855篇 |
2012年 | 2322篇 |
2011年 | 2465篇 |
2010年 | 1846篇 |
2009年 | 1705篇 |
2008年 | 1970篇 |
2007年 | 1823篇 |
2006年 | 1784篇 |
2005年 | 1422篇 |
2004年 | 1140篇 |
2003年 | 1036篇 |
2002年 | 1015篇 |
2001年 | 825篇 |
2000年 | 615篇 |
1999年 | 564篇 |
1998年 | 441篇 |
1997年 | 371篇 |
1996年 | 403篇 |
1995年 | 321篇 |
1994年 | 280篇 |
1993年 | 225篇 |
1992年 | 231篇 |
1991年 | 223篇 |
1990年 | 170篇 |
1989年 | 148篇 |
1988年 | 106篇 |
1987年 | 95篇 |
1986年 | 96篇 |
1985年 | 77篇 |
1984年 | 60篇 |
1983年 | 56篇 |
1982年 | 35篇 |
1981年 | 33篇 |
1980年 | 31篇 |
1978年 | 27篇 |
1977年 | 30篇 |
1976年 | 23篇 |
1974年 | 20篇 |
1973年 | 28篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
Yang M Wang GJ Wang SJ Li XT Xu YP Wang SP Xiang JD Pan SR Cao GX Ye WC 《Rapid communications in mass spectrometry : RCM》2005,19(12):1619-1623
23-Hydroxybetulinic acid is a newly isolated derivative of betulinic acid. The agent exhibits potential anti-tumor activity and functions in this regard via apoptosis. In support of pharmacokinetic and toxicological evaluations, a new assay based on liquid chromatography/mass spectrometry (LC/MS) was developed for the quantitative analysis of 23-hydroxybetulinic acid. Sample preparation consisted of extraction of the plasma by the addition of methylene chloride followed by centrifugation. Aliquots of the supernatant were analyzed using an isocratic reversed-phase high-performance liquid chromatography (HPLC) system coupled to a negative ion electrospray mass spectrometer. Molecules of 23-hydroxybetulinic acid and the internal standard limonin were detected using selected ion monitoring at m/z 471 and 469, respectively. The limit of detection of 23-hydroxybetulinic acid was 0.05 pg (0.11 fmol) injected on-column (10 pg/mL, 5 microL injection volume), and the limit of quantitation was 10 pg (21.19 fmol, 2 ng/mL, 5 muL injection volume). 23-Hydroxybetulinic acid was stable in plasma samples at -20 degrees C for at least 3 weeks. The intra-day and inter-day coefficients of variation of the assay were 3.0 and 4.8%, respectively. The utility of the assay was demonstrated by measuring 23-hydroxybetulinicacid in mouse plasma following intragastric administration (IG) in vivo. Pharmacokinetic parameters were calculated using the 3P97 pharmacokinetic software package. A two-compartment, first-order model was selected for pharmacokinetic modeling. The result showed that after IG of 200 mg/kg 23-hydroxybetulinic acid, the plasma concentrations reached peaks at 2 h with C(max) of 3.1 microg/mL. The 200 mg/kg 23-hydroxybetulinic acid suspension IG doses were found to have long elimination half-lives of 25.6 h and low bioavailability of 2.3%. No interference was noted due to endogenous substances. These analytical methods should be of value in future studies related to the development and characterization of 23-hydroxybetulinic acid. 相似文献
992.
993.
The molar heat capacity of the azeotropic mixture composed of ethanol and toluene was measured by a high precision adiabatic calorimeter from 80 to 320 K. The glass transition and phase transitions of the azeotropic mixture were determined based on the heat capacity measurements. A glass transition at 103.350 K was found. A solid-solid phase transition at 127.282 K, two solid-liquid phase transitions at 153.612 and 160.584 K were observed, which correspond to the transition of metastable crystal to stable crystal of ethanol and the melting of ethanol and toluene, respectively. The thermodynamic functions and the excess ones of the mixture relative to the standard temperature 298.15 K were derived based on the relationships of the thermodynamic functions and the function of the measured heat capacity with respect to temperature. 相似文献
994.
The signal-to-noise level of light emitting diode (LED) fluorimetry using a liquid-core-waveguide (LCW)-based microfluidic capillary electrophoresis system was significantly enhanced using a synchronized dual wavelength modulation (SDWM) approach. A blue LED was used as excitation source and a red LED as reference source for background-noise compensation in a microfluidic capillary electrophoresis (CE) system. A Teflon AF-coated silica capillary served as both the separation channel and LCW for light transfer, and blue and red LEDs were used as excitation and reference sources, respectively, both radially illuminating the detection point of the separation channel. The two LEDs were synchronously modulated at the same frequency, but with 180°-phase shift, alternatingly driven by a same constant current source. The LCW transferred the fluorescence emission, as well as the excitation and reference lights that strayed through the optical system to a photomultiplier tube; a lock-in amplifier demodulated the combined signal, significantly reducing its noise level. To test the system, fluorescein isothiocyanate (FITC)-labeled amino acids were separated by capillary electrophoresis and detected by SDWM and single wavelength modulation, respectively. Five-fold improvement in S/N ratio was achieved by dual wavelength modulation, compared with single wavelength modulation; and over 100-fold improvement in S/N ratio was achieved compared with a similar LCW-CE system reported previously using non-modulated LED excitation. A detection limit (S/N = 3) of 10 nM FITC-labeled arginine was obtained in this work. The effects of modulation frequency on S/N level and on the rejection of noise caused by LED-driver current and detector were also studied. 相似文献
995.
The lower singlet excited states for dimethylaminobenzophenone have been investigated as a function of the twisting motion with inclusion of solvent effects. Theoretical calculations have been performed using time-dependent density functional theory. The B3LYP and MPW1PW91 functionals with a 6-311+G(2d,p) basis set have been used to compute transition energies. The solvent effects have been described within the polarizable continuum model. Ground-state geometries are optimized using density functional theory with both B3LYP and MPW1PW91 functionals combined with 6-31G(d) basis sets. Vertical absorption energy calculations characterize the lower singlet excited states both in vacuum and in different kinds of solvents. A large redshift of the absorption maximum in the polar solvent suggests an intramolecular charge transfer character of the excited state. We have constructed the potential energy curves of two possible twisting motions of the excited states both in vacuum and in the polar solvent of acetonitrile: the twisting of only the dimethylamino group and the twisting of the dimethylaminophenyl group with respect to the benzoyl group. Both twisting processes predict the formation of the twisted intramolecular charge transfer state associated with the crossing of a low barrier. The presence of the polar solvent significantly changes the shape of the energy curves. Calculated emission energies for both the isolated and the solvated systems show a large Stokes shift between the absorption and fluorescence maxima. Two possible twisting motions produce similar fluorescence spectroscopic consequences. Our results including solvent effects explain the weak "dual-fluorescence" feature of dimethylaminobenzophenone, and imply that the two possible twisting motions may occur in the excited-state relaxation dynamics, but the twisting of the dimethylamino group seems to take place easier. 相似文献
996.
Weakly bound linear and bent dimers, FH—X (where X = CO, OC, CNH, NCH, N2O and ON2), are investigated using the DFT B3LYP and ab initio MP2 methods with the same basis sets (6–311++G(3df,2pd)). The strengths of the H—C or H—N H‐bonds in dimers FH—CO, FH—CNH, and FH—N2O are compared with those of the H—O or H—N H‐bonds in dimers FH—OC, FH—NCH, and FH—ON2. The results obtained for the H‐bond distances, the elongation effect of the HF bond, the red shift of the HF stretching frequency, and the energy difference between the dimer and the charge transfer reveal that the H‐bonds of the first group of dimers are stronger than those of the second. The Gibbs energies calculated for the six dimer formations indicate that the weakly bound dimers are unstable at room temperature (T = 298 K) (FH—X's → FH + X's, ΔG < 0). 相似文献
997.
2-Halophenyl ketones 1a-e (1a, o-IC(6)H(4)COCH(3)) undergo carbocyclization with alkyl propiolates (2a, CH(3)(CH(2))(4)C[triple bond]CCO(2)CH(3); 2b, TMSC[triple bond]CCO(2)Et 2c, CH(3)C[triple bond]CCO(2)CH(3); 2d, CH(3)OCH(2)C[triple bond]CCO(2)CH(3); 2e, CH(3)(CH(2))(3)C[triple bond]CCO(2)CH(3); 2f, PhC[triple bond]CCO(2)CH(3); and 2g, (CH(3))(3)C[triple bond]CCO(2)CH(3)) in the presence of Ni(dppe)Br(2) and zinc powder in acetonitrile at 80 degrees C to afford the corresponding indenol derivatives 3a-m with remarkable regioselectivity in good to excellent yields. The nickel-catalyzed carbocyclization reaction was successfully extended to other simple disubstituted alkynes. Thus, the reaction of 2-halophenyl ketones 1a-e with disubstituted alkynes (2h, PhC[triple bond]CPh; 2i, CH(3)C(6)H(4)C[triple bond]CC(6)H(4)CH(3); 2j, CH(3)CH(2)C[triple bond]CCH(2)CH(3); 2k, PhC[triple bond]CCH(3); 2l, TMSC[triple bond]CCH(3); and 2m, PhC[triple bond]C(CH(2))(3)CH(3)) proceeded smoothly to afford the corresponding indenols 4a-t in good to excellent yields. For unsymmetrical alkynes 2k-m, the carbocyclization gave two regioisomers with regioselectivities ranging from 1:2 to 1:12 depending on the substituents on the alkyne and on the aromatic ring of halophenyl ketone. A possible mechanism for this nickel-catalyzed carbocyclization reaction is also proposed. 相似文献
998.
Both STO-3G ab initio and s-p separation-type-modified INDO semiempirical methods were applied to molecular-orbital calculation of the N20 molecule. From these two methods, the optimized bond distances between the nearest N atoms (dn-n) and the most calculated thermodynamic data are close to each other. The positive values of ΔHa° and ΔGa° for the atomization reaction in this work prove that N20 is stable. In contrast to conventional INDO and MINDO/3, but similar to former AMI and MNDO calculations, both ΔHr° and ΔGr° are positive in the formation reaction, which indicates that N20 belongs to the category of high-energy molecules. 相似文献
999.
An accurate and simple HPLC method for the simultaneous determination of three protoberberine alkaloids (columbamine, jatrorrhizine, and palmatine) contained in Chinese medicine Jin-Guo-Lan (Tinospora sagittata Oliv. and Tinospora capillipes Gagnep) is presented in this study. The herb samples from six main origins and three herb markets were investigated. The separation was performed on a YMC-C18 ODS column at 30°C with a gradient elution program. Acetonitrile and phosphate buffer (0.02 mol L−1 sodium dihydrogen phosphate and 0.01 mol L−1 triethylamine, pH 3) were used as mobile phases and the flow rate was set at 1 mL min−1. The recovery of the method was in the range of 99.43–100.96%, and all the alkaloids showed good linearity (r
2 > 0.9997) in the relatively wide concentration ranges. The developed method was applied to the determination of these alkaloids in the collected herb samples, and the results showed that the contents of these components in Jin-Guo-Lan varied greatly from habitat to habitat. It was demonstrated that the proposed method was helpful for the quality evaluation of Chinese medicine Jin-Guo-Lan. 相似文献
1000.
Wei-Cho Huang Cheng S. Gong George T. Tsao 《Applied biochemistry and biotechnology》2003,106(1-3):471-480
Pressure pulsation (PP) was investigated for its effects on oxygen transfer rate (OTR) measured by sulfite oxidation. By manipulating
airflow rate, 0.41–1.2 vvm, and a control valve in a 4-L bioreactor, the frequency of PP was varied at different gas pressures3–15
psig. A mathematical model of OTR was built and compared to experimental data. OTR was also examined at constant gas pressure,
4.5–15.0 psig. The results indicate a good agreement between measurement and model prediction. OTR above 9 psig during PP
showed significant enhancement at 25°C. This proves that PP not only affects the elevation of DO level, but also increases
the interfacial area and mass transfer coefficient. 相似文献