全文获取类型
收费全文 | 59133篇 |
免费 | 851篇 |
国内免费 | 297篇 |
专业分类
化学 | 27611篇 |
晶体学 | 1030篇 |
力学 | 3201篇 |
综合类 | 8篇 |
数学 | 4672篇 |
物理学 | 23759篇 |
出版年
2022年 | 497篇 |
2021年 | 477篇 |
2020年 | 452篇 |
2019年 | 430篇 |
2018年 | 572篇 |
2017年 | 497篇 |
2016年 | 898篇 |
2015年 | 640篇 |
2014年 | 991篇 |
2013年 | 2520篇 |
2012年 | 2344篇 |
2011年 | 3017篇 |
2010年 | 2133篇 |
2009年 | 2183篇 |
2008年 | 2767篇 |
2007年 | 2600篇 |
2006年 | 2466篇 |
2005年 | 2196篇 |
2004年 | 2000篇 |
2003年 | 1765篇 |
2002年 | 1660篇 |
2001年 | 3010篇 |
2000年 | 2154篇 |
1999年 | 1557篇 |
1998年 | 1086篇 |
1997年 | 1058篇 |
1996年 | 896篇 |
1995年 | 789篇 |
1994年 | 706篇 |
1993年 | 626篇 |
1992年 | 958篇 |
1991年 | 948篇 |
1990年 | 850篇 |
1989年 | 747篇 |
1988年 | 731篇 |
1987年 | 799篇 |
1986年 | 657篇 |
1985年 | 888篇 |
1984年 | 832篇 |
1983年 | 570篇 |
1982年 | 569篇 |
1981年 | 537篇 |
1980年 | 503篇 |
1979年 | 622篇 |
1978年 | 653篇 |
1977年 | 665篇 |
1976年 | 580篇 |
1975年 | 484篇 |
1974年 | 525篇 |
1973年 | 451篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
831.
M Horie K Saito Y Hoshino N Nose N Hamada H Nakazawa 《Journal of chromatography. A》1990,502(2):371-378
A simple and selective method for the determination of sulphamethazine (SMT) and its metabolite, N4-acetylsulphamethazine (N4-AcSMT), in meat by high-performance liquid chromatography (HPLC) with photodiode-array detection was developed. The drugs were extracted from meat with 0.2% metaphosphoric acid-methanol (6:4), followed by a Bond-Elut C18 clean-up procedure. The HPLC separation was carried out on a Supersphere RP-18e column (125 X 4.0 mm I.D.) using 0.05 M sodium dihydrogenphosphate (pH 4.5)-acetonitrile (8:2) as the mobile phase at a flow-rate of 0.5 ml/min, and monitored with a photodiode-array detector. The recoveries of SMT and N4-AcSMT from meat fortified at 0.5 micrograms/g were 90.1-93.3 and 93.0-94.4%, respectively, with coefficients of variation of 1.9-3.2 and 1.5-2.7%. The limits of detection were 0.02 micrograms/g for each drug. SMT was found in ten samples of imported meat (12.5%) at levels ranging from 0.05 to 1.05 micrograms/g. 相似文献
832.
Zhao X Chiang CY Miller ML Rampersad MV Darensbourg MY 《Journal of the American Chemical Society》2003,125(2):518-524
The established ability of the Fe(II) bridging hydride species (micro-H)(micro-pdt)[Fe(CO)2(PMe3)]2+, 1-H+, to take-up and heterolytically activate dihydrogen, resulting in H/D scrambling of H2/D2 and H2/D2O mixtures (Zhao et al. Inorg. Chem. 2002, 41, 3917) has prompted a study of simultaneous alkene/H2 activation by such [Fe]H2ase model complexes. That the required photolysis produced an open site was substantiated by substitution of CO in 1-H+ by CH3CN with formation of structurally characterized [(micro-H)(micro-pdt)[Fe(CO)2(PMe3)][Fe(CO)(CH3CN)(PMe3)]]+[PF6]-. Under similar photolytic conditions, H/D exchange reactions between D2 and terminal alkenes (ethylene, propene and 1-butene), but not bulkier alkenes such as 2-butene or cyclohexene, were catalyzed by 1-H+ and the edt (SCH2CH2S) analogue, 2-H+. Substantial regioselectivity for H/D exchange at the internal vinylic hydrogen was observed. The extent to which the olefins were deuterium enriched vs deuterated was catalyst dependent. The stabilizing effect of the binuclear chelating ligands, SCH2CH2CH2S, pdt, and SCH2CH2S, edt, is required for the activity of binuclear catalysts, as the mono-dentate micro-SEt analogue decomposed to inactive products under the photolytic conditions of the catalysis. Reactions of 1 and 2 with EtOSO2CF3 yielded the S-alkylated products, [(micro-SCH2CH2CH2SEt)[Fe(CO)2(PMe3)]2]+[SO3CF3]- (1-Et+), and 2-Et+, rather than micro-C2H5 analogues to the micro-H of 1-H+. The stability and lack of reactivity toward H2 of 1-Et+ and 2-Et+, indicates they are not on the reaction path of the olefin/D2 H/D exchange process. A mechanism with olefin binding to an open site created by CO loss and formation of an Fe-(CH2CHDR) intermediate is indicated. A likely role of a binuclear chelate effect is implicated for the unique S-XXX-S cofactor in the active site of [Fe]H2ase. 相似文献
833.
Determination of cadmium in water samples by graphite furnace atomic absorption spectrometry after cloud point extraction 总被引:3,自引:0,他引:3
The formation of a complex with 2-(5-brom-2-pyridylazo)-5-(diethylamino)-phenol (5-Br-PADAP) and cloud point extraction have
been applied to the preconcentration of cadmium followed by its determination by graphite furnace atomic absorption spectrometry
(GFAAS) using octylphenoxypolyethoxyethanol (TritonX-114) as surfactant. The chemical variables affecting the separation were
optimized. At pH 7.0, preconcentration of only 10 mL of sample in the presence of 0.05% TritonX-114 and 2.5 × 10−6 M 5-Br-PADAP enabled the detection of 0.04 μg/L cadmium. The enrichment factor was 21 for cadmium. The regression equation
was A = 0.0439C(μg/L) + 7.2 × 10−3. The correlation coefficient was 0.9995. The precision for 10 replicate determinations at 10 μg/L Cd was 2.7% relative standard
deviation (RSD). The proposed method has been applied to the determination of cadmium in water samples.
The text was submitted by the authors in English. 相似文献
834.
A reversed-phase liquid chromatographic (RPLC) method has been developed for determination of arabinosylcytosin (Ara-C) and
its metabolite 1-β-D-arabinofuranosyluracil (Ara-U) on a 250 mm × 4.6 mm i.d., 5 μm particle, Diamonsil C18 column. The mobile phase was a mixture of 5% methanol and 95% 10 mmol L−1 phosphate buffer adjusted to pH 5.5. The flow-rate was 1.0 mL min−1 and the injection volume 20 μL. Eluting compounds were detected at 270 nm by use of an ultraviolet detector. Under these
LC conditions cyclophosphamide (CTX) and pirarubicin (THP), two other medicines given with Ara-C in clinical treatment, do
not interfere with measurement of Ara-C and Ara-U. Individual calibration plots of peak area against concentration generated
from analysis of standard solutions were used to calculate the concentrations of Ara-C and Ara-U in sample solutions. The
calibration plot was linear in the range 2.5–100 μg mL−1, the average recovery of Ara-C and Ara-U was more than 98% (RSD < 2.5%), and between-day and within-day precision, expressed as relative standard deviation (RSD), were below 4.0%. LOQ for both Ara-C and Ara-U was 2 μg mL−1. The method is rapid, simple, accurate and reproducible, and especially useful for application to patient samples. 相似文献
835.
Y Nomoto H Takai T Hirata M Teranishi T Ohno K Kubo 《Chemical & pharmaceutical bulletin》1991,39(1):86-90
A series of 1-(6,7-dimethoxy-4-quinazolinyl)piperidines carrying various 5-membered heterocycles at the 4-position was synthesized and examined for cardiotonic activity in anesthesized dogs. The (4-oxo-2-thioxo-3-imidazolindinyl)amino derivatives showed the most potent inotropic activity. Marked loss of activity was observed in the 2,4-dihydro-3-thioxo-3H-1,2,4-triazolyl, the 2,4-dihydro-3-oxo-3H-pyrazolyl and the (2,3-dihydro-2-thioxo-3H-1,3,4-thiadiazol-5-yl)amino derivatives. The synthesis and structure-activity relationships are discussed. 相似文献
836.
T. Dresch H. Kramer Y. Thurner R. Weber 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,18(4):391-397
Photodissociation of negatively charged sulfur dioxide clusters (SO2) n ? , 2≦n≦11, was investigated in the wavelength range between 458 nm and 600 nm using a tandem mass spectrometer. The spectral position of the absorption band remains unchanged, however it exhibits narrowing with increasing cluster size. The smooth evolution of the spectra shows that the clusters are composed of a dimer anion core surrounded by neutral molecules. The analysis of the fragmentation products reveals that the absorption of a photon is followed by statistical evaporation of neutrals with a mean energy loss of 0.28±0.05 eV per evaporated monomer in the large cluster limit. 相似文献
837.
H Fujita Y Sasaki H Kohno Y Ohkubo A Ambo K Suzuki M Hino 《Chemical & pharmaceutical bulletin》1990,38(8):2197-2200
Nine analogs based on a structure of Tyr-D-Arg-Phe-X (X = alkylamides or alkylhydrazide containing electron-withdrawing atoms or groups) were newly synthesized and their biological properties were examined by the opioid receptor binding properties of mu-, delta- and kappa-receptors, guinea-pig ileum (GPI) assay and analgesic activity in the tail pinch test after subcutaneous administration in mice. Analogs with X = NHCF2CF3, Sar-ol, or NH(CH2)2CN showed potent activities in the GPI and analgesic assays and high affinity for mu-receptor. An analog with X = taurinamide was found to possess 4-fold higher mu-receptor selectivity than that of [D-Ala2, MePhe4, Gly-ol5]enkephalin (DAGO). The receptor binding properties of previously reported analogs [Chem. Pharm. Bull., 33, 1528 (1985); ibid., 33, 4865 (1985); ibid., 36, 4834 (1988)] were also examined for overall discussion of the structure-activity relationships of this series of tripeptide amides. 相似文献
838.
Abstract— The weak and reversible binding of the antifungal drug, griseofulvin (GF), to calf thymus DNA has been demonstrated by difference spectroscopy and the quenching of the fluorescence of GF by DNA observed. The value of K n was determined to be 800 M -1 by fluorescence quenching titration. Adenosine and guanosine also exhibit difference spectra with GF and quench GF fluorescence indicating that they may be the site of both binding and energy transfer. The in vitro photosensitization of DNA by griseofulvin is shown to occur. It is proposed that the clinically observed in vivo photosensitizing action of griseofulvin may result from binding followed by excitation energy transfer and that this may also be important in the antifungal activity of the drug. 相似文献
839.
J. J. Zhang L. G. Ge X. L. Zhang Y. J. Dai H. L. Chen L. P. Mo 《Journal of Thermal Analysis and Calorimetry》1999,58(2):269-278
The thermal decomposition of Zn[NFA]25H2O (NFA=C16H18FN3O3, norfloxacin) and its kinetics were studied under non-isothermal conditions in air by TG-DTG and DTA methods. The intermediate and residue for each decomposition were identified from the TG curve. The non-isothermal kinetic data were analyzed by means of the Achar method and the Madhusudanan-Krishnan-Ninan (MKN) method. The possible reaction mechanisms were investigated by comparing the kinetic parameters. The kinetic equation for the second stage can be expressed as d/dt=Aexp(–E/RT)(1–).This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
840.
WADOOD Y. HAMAD 《Cellulose (London, England)》1997,4(1):51-56
Wood-pulp fibres are recognized as concentrically-layered, laminated composite tubes of structural reinforcing material, the
cellulose microfibrils, embedded in a cementing matrix of hemicellulose and lignin. When the single fibres are subjected to
cyclic mechanical action, their morphological behaviour is characterized by the fatigue growth of micro-voids and surface
damage which individually and collectively give rise to stress concentrations, and eventually crack development. The progressive
damage phenomena, evinced by the surface imaging and optical sectioning techniques through utilizing confocal laser scanning
microscopy, are understood to be consequences of the cumulative material micromechanical degradation and subsequent microstructural
breakdown of the cellulose microfibrillar framework. This structural breakdown is believed to effect the fibrillation and
flexibilization of the fibres
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献