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31.
Lindsey?Gillian?MackayEmail author C.?Peter?Taylor Richard?Bruce?Myors Ruth?Hearn Bernard?King 《Accreditation and quality assurance》2003,8(5):191-194
The selection of an appropriate isotope dilution mass spectrometry technique for the practical application of this potentially primary method of analysis is highly important. The NARL approach for the application of the exact matching double isotope dilution mass spectrometry technique developed by Henrion is presented. NARL's approach utilises exact matching to minimise the effect of measurement biases within the method but also includes the thorough examination of all other biasing factors. The approach has been successfully tested in international CCQM intercomparisons with other national metrology institutes. 相似文献
32.
Abstract— The quenching by oxygen of the α- and β-phosphorescence of trypaflavine adsorbed on silica gel has been found to obey the simple Stern-Volmer relationship for oxygen partial pressures up to the point at which, for low temperatures, the β-phosphorescence becomes negligible. At room temperatures above this partial pressure the Stern-Volmer plot is no longer linear. An explanation is proposed, based on the formation of a triplet-oxygen complex, analogous to that proposed by Porter and Wright for paramagnetic quenching. 相似文献
33.
The effects of crystallinity, orientation and degree of polymerization on the vacuum pyrolysis of cellulose have been investigated. Natural, modified and manmade celluloses were characterized and the kinetics of their pyrolysis at 251°C studied. The high-temperature pyrolysis of these samples was also investigated by means of DSC and TGA. At 251°C all of the samples showed a rapid, initial weight loss followed by a linear (weight loss)1/2 versus time dependency. Both the initial weight loss and the subsequent reaction rate were dependent upon the crystallinity of the sample. The reaction rate was shown to be inversely proportional to (DP)1/2 and related to the orientation. Effects of crystallinity and orientation could also be seen in the DSC thermograms and in the apparent energies of activation. Results are interpreted in terms of probable mechanisms of the uncatalyzed pyrolysis of cellulose. 相似文献
34.
Ruth Freitag Thomas Baltes Martin Eggert 《Journal of polymer science. Part A, Polymer chemistry》1994,32(16):3019-3030
Several batches of poly-N,N-diethylacrylamide were synthesized by anionic and by group transfer polymerization (GTP). A radical poly-N,N-diethylacrylamide prepared from the same monomer was also included in the comparison. According to matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) both types of living polymerization resulted in narrow molecular weight distributions with Mw/Mn values below 1.5. Average molecular weights (Mn) between 888 and 4678 g/mol were calculated in these cases. The radical polymer had an average molecular weight (Mn) of approximately 130,000 g/mol. The dry anionic and GTP polymers were investigated by differential scanning calorimetry (DSC) and x-ray diffraction spectrometry. Evidence for partial crystallinity in the solid state was found. The conformation of all polymers was examined by high resolution (600 MHz) NMR. According to these measurements, 75% of the ? CHR? groups of the anionic poly-N,N-diethylacrylamide were located in an isotactic triade. The remaining 25% had heterotactic structure, while no indication for the presence of syndiotactic protons was found. Poly-N,N-diethylacrylamide prepared by GTP, on the other hand, had mainly syndiotactic structure. The aqueous solutions of the polymers showed phase separation upon heating. Whereas the lower critical solution temperature (LCST) was approximately 30°C in the case of the poly-N,N-diethylacrylamide prepared by GTP and by radical polymerization, uncommonly high LCSTs of more than 40°C were observed for the anionic poly-N,N-diethylacrylamide. © 1994 John Wiley & Sons, Inc. 相似文献
35.
Barro R Ares S Garcia-Jares C Llompart M Cela R 《Analytical and bioanalytical chemistry》2005,381(1):255-260
A combination of sorbent enrichment and ultrasound-assisted solvent extraction has been used to determine polychlorinated biphenyls in air. Analytes were sampled by pumping a known volume of air through a porous polymer (Tenax TA). The enriched adsorbent was transferred into a glass vial, and ultrasound-assisted extraction of the analytes was then performed in n-hexane. Quantification was carried out by using gas chromatography coupled to tandem mass spectrometry. Breakthrough volume of the sampling step was studied, indicating that 10 m3 of air could be processed without losses of the most volatile compounds. Good recoveries (75–96%) were obtained, and limits of detection at the sub ng m–3 were achieved for all the analytes. The proposed method is very simple and fast, avoiding the use of large solvent volumes and time-consuming preconcentration steps. 相似文献
36.
Dong Xiao Brian J. Lavey Anandan Palani Robert G. Aslanian Neng-Yang Shih Gerard P. Randolph Ruth A. Duffy 《Tetrahedron letters》2005,46(44):7653-7656
Unlike the lithiation of N-Boc-2-alkylpiperidines, which occurs at the 6-position, N-Boc-2-phenylpiperidine and N-Boc-2-phenylpyrrolidine can be lithiated exclusively at the 2-position. The tertiary carbanions can be trapped with a variety of electrophiles. This chemistry was used for the synthesis of a potent NK1 ligand (Ki = 0.3 nM). The bioactive configuration at the piperidine quaternary center was determined by X-ray analysis to be (S). 相似文献
37.
Yu. Arestov A. Borovikov E. Kozlovsky A. Minaenko A. Moiseev C. Cochet D. Denegri C. Lewin M. A. Turluer U. Gensch H. J. Grabosch W. Lohmann J. MacNaughton France-USSR Collaboration CERN-USSR Collaboration 《Zeitschrift fur Physik C Particles and Fields》1981,8(4):283-289
New data on the inclusive production of the non-strange resonances ?0(770), ω(783), ?(1020) andf(1270) inK ? p interactions at 32 GeV/c are presented. The inclusive production cross sections are equal to (4.32±0.72) mb, (3.7±1.4) mb, (0.65±0.10) mb and (0.91±0.35) mb respectively. Estimates of the topological cross sections are also obtained. The invariant and non-invariantx-distributions for the vector mesons ?0 and ? indicate the prevalence of forward resonance production in the c.m. system. For the tensorf-meson the rapidity andx-distributions are presented. Thet′-distributions for ?0, ?, andf have exponential slopes of 0.6±0.1 GeV?2, 1.2±0.2 GeV?2, and 0.8±0.5 GeV?2 respectively. The exponential slope ofp T 2 -distribution of thef-meson is equal to (2.3±0.5) GeV?2. 相似文献
38.
39.
The dithiocarbene complex W(CO)5[C(SCH3)2 reacts with tertiary phosphines, PPh2CH3, PPh(CH3)2, P(C2H5)3 and P(OCH3)3 to form the phosphorane complexes W(CO)5[CH3S)2C-PR3] and with HPPh2 to form the phosphine complex W(CO)5[PPh2[CH(SCH3)2]. Kinetic studies of both types of reactions show that their rates are first order each in W(CO)5[C(SCH3)2] and in the phosphorus ligand. A mechanism involving rate determining phosphorus attack at the carbene carbon followed by rapid rearrangement to the product is consistent with this rate law. Rate constants for the reactions increase with increasing nucleophilicities of the phosphines: P(OCH3)3 < PPh2H < PPh2CH3 ? PPh(CH3)2 < P(C2H5)3. The ΔH values decrease (P(OCH3)3 > PPh2H > PPh2(CH3) > PPh(CH3)2 > P(C2H5)3) as the nucleophilicities of the phosphines increase. The ΔS values (≈-30 e.u.) remain essentially constant for all the reactions. The cyclic dithiorcarbenes W(CO)5[CS(CH2)nS], wheren- 3 or 4, react with PPh2(CH3) to form the cyclic phosphorane complexes, W(CO)5[S(CH2)nSC-PPh2(CH3)]. The 6- and 7- membered cyclic dithiocarbenes also react with PPh2H to form the phosphine complexes, W(CO)5 {PPh2- [CS(CH2)nS(H)]}. 相似文献
40.