全文获取类型
收费全文 | 4879篇 |
免费 | 223篇 |
国内免费 | 3篇 |
专业分类
化学 | 3404篇 |
晶体学 | 46篇 |
力学 | 85篇 |
数学 | 722篇 |
物理学 | 848篇 |
出版年
2023年 | 42篇 |
2022年 | 23篇 |
2021年 | 58篇 |
2020年 | 96篇 |
2019年 | 75篇 |
2018年 | 101篇 |
2017年 | 107篇 |
2016年 | 184篇 |
2015年 | 157篇 |
2014年 | 169篇 |
2013年 | 339篇 |
2012年 | 390篇 |
2011年 | 447篇 |
2010年 | 213篇 |
2009年 | 173篇 |
2008年 | 322篇 |
2007年 | 331篇 |
2006年 | 276篇 |
2005年 | 274篇 |
2004年 | 222篇 |
2003年 | 182篇 |
2002年 | 146篇 |
2001年 | 135篇 |
2000年 | 114篇 |
1999年 | 66篇 |
1998年 | 43篇 |
1997年 | 25篇 |
1996年 | 50篇 |
1995年 | 34篇 |
1994年 | 32篇 |
1993年 | 33篇 |
1992年 | 40篇 |
1991年 | 23篇 |
1990年 | 10篇 |
1989年 | 8篇 |
1988年 | 15篇 |
1987年 | 10篇 |
1986年 | 12篇 |
1985年 | 16篇 |
1984年 | 16篇 |
1983年 | 10篇 |
1982年 | 19篇 |
1981年 | 13篇 |
1980年 | 8篇 |
1979年 | 9篇 |
1978年 | 6篇 |
1976年 | 5篇 |
1975年 | 4篇 |
1974年 | 4篇 |
1973年 | 4篇 |
排序方式: 共有5105条查询结果,搜索用时 15 毫秒
101.
A reinvestigation of the NMR spectra of the complexes (NBu4)2[M2(mu-LL)2R4] (M = Pd, Ni, Pt, LL = pyrazolate (pz), 3,5-dimethylpyrazolate (dmpz), 3-methylpyrazolate (mpz), indazolate (indz), R = C6F5; M = Pd, LL = pz, dmpz, mpz, indz, R = 2,4,6-C6F3H2) shows that the boat-shaped dimeric structures of their anions are quite stable in solution, and the previously proposed fast equilibria or dissociations to give species such as [R2M(N-N)(acetone)]-, [R2M(acetone)2] + 2dmpz-, or [R2M(N1-N2)(acetone)]- + [R2M(N2-N1)(acetone)]- in no case occur. A mixture of the two diastereoisomers (head-to-head, HH, and head-to-tail, HT) is present for the asymmetrically substituted azolates (mpz and indz), in a ratio ranging from 1:7 to 1:30 for the different complexes. Strong through-space coupling between the endo ortho fluorine nuclei of different MR2 fragments is observed in the 19F NMR spectra of these diastereoisomers whose boatlike structures place these atoms at short distances. 相似文献
102.
Today’s nuclear curricula have the purpose to fulfil labor requirements of the nuclear market, both power and applications,
as well as keeping up the academic level required for research and development in nuclear sciences. This work analyses the
power and applications markets and the situation of nuclear education in several countries, including Mexico, as well as collective
efforts promoted by the International Atomic Energy Agency (IAEA) and other organizations. Conclusions are obtained about
the status and trends in nuclear education, emphasizing the role of the academic and users sectors to fit the future demand
and the availability of skilled personnel. 相似文献
103.
Mayneris J Martínez R Hernando J Gray SK González M 《The Journal of chemical physics》2008,128(14):144302
Extensive quantum real wave packet calculations within the helicity decoupling approximation are used to analyze the influence of the HF vibrational excitation on the K+HF(v=0-2,j=0)-->KF+H reaction. Quantum reaction probabilities P and reaction cross sections sigma are compared with corresponding quasiclassical trajectory (QCT) results. Disregarding threshold regions for v=0 and 1 (v=2 has no threshold), both approaches lead to remarkably similar results, particularly for sigma, validating the use of the QCT method for this system. When moving from v=0 to v=1 there is a large increase in P and sigma, as expected for a late barrier system. For v=2 the reaction becomes exoergic and P approximately 0.95 (with the exception of large total angular momenta where centrifugal barriers play a role). While substantial vibrational enhancement of the reactivity is thus seen, it is still quite less than that inferred from experimental data in the intermediate and high collision energy ranges. The origin of this discrepancy is unclear. 相似文献
104.
Gagliardi LG Castells CB Ràfols C Rosés M Bosch E 《Journal of separation science》2008,31(6-7):969-980
We propose a general simple equation for accurately predicting the retention factors of ionizable compounds upon simultaneous changes in mobile phase pH and column temperature at a given hydroorganic solvent composition. Only four independent experiments provide the input data: retention factors measured in two pH buffered mobile phases at extreme acidic and basic pH values (e. g., at least +/- 2 pH units far from the analyte pK(a)) and at two column temperatures. The equations, derived from the basic thermodynamics of the acid-base equilibria, additionally require the knowledge of the solute pK(a )and enthalpies of acid-base dissociation of both the solute and the buffer components in the hydroorganic solvent mixture. The performance of the predictive model is corroborated with the comparison between theoretical and experimental retention factors of several weak acids and bases of important pharmacological activity, in mobile phases containing different buffer solutions prepared in 25% w/w ACN in water and at several temperatures. 相似文献
105.
We report a DFT study on the self‐assembly of the fullerene derivative PCBM on the Au(111) surface. Recent STM experiments (Angew. Chem. 2007 , 119, 8020–8023[1]) show a coverage‐dependent transition of the adsorption and self‐assembly of PCBM on this surface. To understand the origin of this observation, we compute the geometries and relative energies of ten PCBM dimers and four tetramers. The calculations show that the self‐assembly of PCBM at high coverage is mainly controlled by hydrogen bonding between the PCBM tails. Due to the large size of the fullerene cage, the hydrogen bonds are formed far away from the surface; hence they are very similar to those found in the gas phase. This picture successfully explains the observed site‐insensitive adsorption at high coverage and the 2D arrangement of PCBM on the surface. 相似文献
106.
Hernández C Fernández M Quejido AJ Sánchez DM Morante R Martín R 《Analytica chimica acta》2006,571(2):279-287
Isotope dilution-thermal ionisation mass spectrometry (ID-TIMS) analysis has been applied to the determination of tin in a fly ash sample supplied by the EC Joint Research Centre (Ispra, Italy). The proposed procedure includes the silica gel/phosphoric acid technique for tin thermal ionisation activation and a strict heating protocol for isotope ratio measurements. Instrumental mass discrimination factor has been previously determined measuring a natural tin standard solution. Spike solution has been prepared from 112Sn-enriched metal and quantified by reverse isotope dilution analysis. Two sample aliquots were spiked and tin was extracted with 4.5 M HCl during 25 min ultrasound exposure time. Due to the complex matrix of this fly ash material, a two-step purification stage using ion-exchange chromatography was required prior TIMS analysis. Obtained results for the two sample-spike blends (10.11 ± 0.55 and 10.50 ± 0.64 μmol g−1) are comparable, both value and uncertainty. Also a good reproducibility is observed between measurements. The proposed ID-TIMS procedure, as a primary method and due to the lack of fly ash reference materials certified for tin content, can be used to validate more routine methodologies applied to tin determination in this kind of samples. 相似文献
107.
Mezcua M Ferrer C García-Reyes JF Martínez-Bueno MJ Albarracín M Claret M Fernández-Alba AR 《Rapid communications in mass spectrometry : RCM》2008,22(9):1384-1392
In this work, two analytical methods based on liquid chromatography coupled to electrospray time-of-flight mass spectrometry (LC/ESI-TOFMS) and tandem mass spectrometry (LC/ESI-MS/MS) are described for the identification, confirmation and quantitation of three insecticides non-authorized in the European Union (nitenpyram, isocarbophos and isofenphos-methyl) but detected in recent monitoring programmes in pepper samples. The proposed methodologies involved a sample extraction procedure using liquid-liquid partition with acetonitrile followed by a cleanup step based on dispersive solid-phase extraction. Recovery studies performed on peppers spiked at different fortification levels (10 and 50 microg kg(-1)) yielded average recoveries in the range 76-100% with relative standard deviation (RSD) (%) values below 10%. Identification, confirmation and quantitation were carried out by LC/TOFMS and LC/MS/MS using a hybrid triple quadrupole linear ion trap (QqLIT) instrument in multiple-reaction monitoring (MRM) mode. The obtained limits of quantitation (LOQs) were in the range 0.1-5 microg kg(-1), depending on each individual technique. Finally, the proposed methods were successfully applied to the analysis of suspected pepper samples. 相似文献
108.
Nozal MA Bernal JL Martín MA Bernal J Alvaro A Martín R Higes M 《Journal of chromatography. A》2008,1190(1-2):224-231
In this work a new liquid chromatography with diode array detection and electrospray ionization mass spectrometry (LC-DAD-ESI-MS) method has been developed for the determination of fumagillin residues in honey. This procedure involves a solid-phase extraction on polymeric cartridges for the isolation of fumagillin from diluted honey. Chromatographic separation of fumagillin was performed in isocratic mode, on a C(18) column (150 mm x 4.60mm i.d., 5 microm), the mobile phase consisted of a mixture of ammonium formate 20mM in water and acetonitrile (61/39, v/v), at 35 degrees C and the flow rate was set at 1.0 mL/min. Average analyte recoveries, influenced by the botanical origin were from 88 to 96% in replica sets of fortified honey samples. The detection limits of the LC-DAD-ESI-MS method were between 24 and 1 microg/kg for clear honeys (rosemary) and between 45 and 4 microg/kg for dark honeys (heather). The developed method has been applied to the analysis of fumagillin residues in honey samples collected from veterinary treated beehives, infected by Nosema ceranae and fed with the technical product at different doses. 相似文献
109.
Febles M Pérez-Hernandez N Pérez C Rodríguez ML Foces-Foces C Roux MV Morales EQ Buntkowsky G Limbach HH Martín JD 《Journal of the American Chemical Society》2006,128(31):10008-10009
Water molecules confined inside narrow pores are of great importance in understanding the structure, stability, and function of water channels. Here we report that besides the H-bonding water that structures the pore, the permanent presence of a significant, fast-moving fraction of incompletely H-bonded water molecules inside the pore should control the free entry and exit of water. This is achieved by means of complementary DSC and solid-state NMR studies. We also present compelling evidence from X-ray diffraction data that the cluster formed by six water molecules in the most stable cage-like structure is sufficiently hydrophobic to be stably adsorbed in a nonpolar environment. 相似文献
110.
Miguel Gd Pérez-Morales M Martín-Romero MT Muñoz E Richardson TH Camacho L 《Langmuir : the ACS journal of surfaces and colloids》2007,23(7):3794-3801
The molecular organization of a mixed film, containing a water-soluble tetracationic porphyrin (TMPyP) and a p-tert-butyl calix[8]arene octacarboxylic acid derivative (C8A), at the air-water interface and on a solid support (LB film), has been investigated. Although the TMPyP aggregation was not detected at the air-water interface, TMPyP J-aggregates have been found in the LB films (Y-type). Unlike tetraanionic porphyrins, for example TSPP, the TMPyP J-aggregates are not induced by a zwitterion formation. The TMPyP J-aggregation is a result of a "double comb" configuration, where porphyrins from opposite layers are interwoven in a linear infinite J-aggregate. Our results confirm that TMPyP molecules tend to self-aggregate strongly, provided the electrostatic repulsions of their peripheral groups are cancelled by the anionic groups of the C8A matrix. 相似文献