全文获取类型
收费全文 | 8287篇 |
免费 | 378篇 |
国内免费 | 34篇 |
专业分类
化学 | 5861篇 |
晶体学 | 35篇 |
力学 | 257篇 |
数学 | 1408篇 |
物理学 | 1138篇 |
出版年
2023年 | 48篇 |
2022年 | 66篇 |
2021年 | 114篇 |
2020年 | 151篇 |
2019年 | 153篇 |
2018年 | 129篇 |
2017年 | 93篇 |
2016年 | 283篇 |
2015年 | 231篇 |
2014年 | 280篇 |
2013年 | 500篇 |
2012年 | 546篇 |
2011年 | 621篇 |
2010年 | 388篇 |
2009年 | 353篇 |
2008年 | 522篇 |
2007年 | 528篇 |
2006年 | 505篇 |
2005年 | 515篇 |
2004年 | 413篇 |
2003年 | 366篇 |
2002年 | 324篇 |
2001年 | 112篇 |
2000年 | 92篇 |
1999年 | 105篇 |
1998年 | 71篇 |
1997年 | 78篇 |
1996年 | 90篇 |
1995年 | 64篇 |
1994年 | 47篇 |
1993年 | 43篇 |
1992年 | 34篇 |
1991年 | 46篇 |
1990年 | 32篇 |
1989年 | 44篇 |
1988年 | 24篇 |
1986年 | 23篇 |
1985年 | 52篇 |
1984年 | 57篇 |
1983年 | 35篇 |
1982年 | 59篇 |
1981年 | 36篇 |
1980年 | 51篇 |
1979年 | 46篇 |
1978年 | 51篇 |
1977年 | 40篇 |
1976年 | 41篇 |
1975年 | 31篇 |
1974年 | 36篇 |
1973年 | 26篇 |
排序方式: 共有8699条查询结果,搜索用时 0 毫秒
81.
Why carry out medicinal chemistry at a university, when it means competing with the billion-dollar research efforts of the pharmaceutical industry? In academic research, the race to get a drug to market is not the prime motivation. Instead, university-based medicinal chemistry is driven by the search for new knowledge and the opportunity to educate a new generation of chemists. Furthermore, academia can complement commercial efforts by addressing diseases neglected by private industry. 相似文献
82.
A novel solid-state NMR concept is introduced that allows for the detection of through-space proton-proton contacts in high spectral resolution. The proposed method not only can be utilized to infer sequential assignments and backbone or side chain conformation in solid-phase polypeptides, but it also provides information about the three-dimensional arrangement of the molecule of interest. As a result, the molecular structure can be studied without additional restrictions regarding sample labeling or magic angle spinning rates. 相似文献
83.
Frère P Allain M Elandaloussi el H Levillain E Sauvage FX Riou A Roncali J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(4):784-792
The electrochemical and chemical oxidation of extended TTF 4 and 5 are analysed by cyclic voltammetry, Visible/NIR and ESR spectroscopies, and the X-ray structures of the new salts 5 x BF(4)(CH(2)Cl(2)) and 4 x ClO(4)(THF)(1/2) are presented. The effects of structural factors on the pi-dimerization or the disproportionation reaction of the cation radical are shown. The oxidation of compound 4 presents the successive formation of stable cation radical and dication species both in dichloromethane (DCM) and in a CH(3)CN/THF mixture. In contrast, for compound 5, the stability of the oxidation states strongly depends on the nature of the solvent. In DCM, the oxidation of 5 proceeds by two close one-electron transfers while in CH(3)CN/THF the dication is directly formed via a two-electron process. The X-ray structures of the two salts reveal the formation of pi-dimers of cation radical. While the dimer (5(2))(2+) is due mainly to pi-pi interactions between the conjugating spacer, the multiplication of the sulfur atoms in compound 4 contributes to stabilize the dimer by the combined effects of S-S and pi-pi interactions. Visible/NIR and ESR experiments confirm the higher tendency of 4(+)(.) to dimerize with the occurrence of dimer and monomer in solution, while for 5(+)(.) only the monomer is detected in DCM. On the other hand, by dissolution of 5 x BF(4)(CH(2)Cl(2)) in CH(3)CN, only the neutral and the dicationic states of compounds 5 are observed owing to the disproportionation reaction. 相似文献
84.
Zhang H Garland M Zeng Y Wu P 《Journal of the American Society for Mass Spectrometry》2003,14(11):1295-1305
A method is proposed, on the basis of a recently developed algorithm--Band Target Entropy Minimization (BTEM)--to reconstruct mass spectra of pure components from mixture spectra. This method is particular useful in dealing with spectral data with discrete features (like mass spectra). Compared to the original BTEM, which has been applied to differentiable spectroscopies such as Fourier-transfer infrared spectroscopy (FTIR), ultraviolet (UV), Raman, and nuclear magnetic resonance (NMR), the latest modifications were obtained through: (1) Reformulating the objective function using the peak heights instead of their derivatives; (2) weighting the abstract vector VT to reduce the effect of noise; (3) using a two-peak targeting strategy (tBTEM) to deal with strongly overlapping peaks; and (4) using exhaustive search to locate all the component spectra. A set of 50 multi-component mass spectra was generated from ten reference experimental pure component spectra. Many of the compounds chosen have common MS fragments and therefore, many of the pure component spectra have considerable intensity in same data channels. In addition, a set of MS spectra from a real system with four components was used to examine the newly developed algorithm. Successful reconstruction of the ten component spectra of the simulated system and the four component spectra of the real system was rapidly achieved using the new tBTEM algorithm. The advantages of the new algorithm and its implication for rapid system identification of unknown mixtures are readily apparent. 相似文献
85.
Holzwarth AR Müller MG Niklas J Lubitz W 《The journal of physical chemistry. B》2005,109(12):5903-5911
The fluorescence kinetics of photosystem I core particles from Chlamydomonas reinhardtii have been measured with picosecond resolution in order to test a previous hypothesis suggesting a charge recombination mechanism for the early electron-transfer steps and the fluorescence kinetics (Müller et al. Biophys. J. 2003, 85, 3899-3922). Performing global target analyses for various kinetic models on the original fluorescence data confirms the "charge recombination" model as the only acceptable one of the models tested while all of the other models can be excluded. The analysis allowed a precise determination of (i) the effective charge separation rate constant from the equilibrated reaction center excited state (438 ns(-1)) confirming our previous assignment based on transient absorption data (Müller et al. Biophys. J. 2003, 85, 3899-3922), (ii) the effective charge recombination rate constant back to the excited state (52 ns(-1)), and (iii) the intrinsic secondary electron-transfer rate constant (80 ns(-1)). The average energy equilibration lifetime core antenna/RC is about 1 ps in the "charge recombination" model, in agreement with previous transient absorption data, vs the 18-20 ps energy transfer lifetime from antenna to RC within "transfer-to-the-trap-limited" models. The apparent charge separation lifetime in the recombination model is about three times faster than in the "transfer-to-the-trap-limited" model. We conclude that the charge separation kinetics is trap-limited in PS I cores devoid of red antenna states such as in C. reinhardtii. 相似文献
86.
Cell lysis was demonstrated on a microfluidic CD (Compact Disc) platform. In this purely mechanical lysis method, spherical particles (beads) in a lysis chamber microfabricated in a CD, cause disruption of mammalian (CHO-K1), bacterial (Escherichia coli), and yeast (Saccharomyces cerevisiae) cells. Interactions between beads and cells are generated in the rimming flow established inside a partially filled annular chamber in the CD rotating around a horizontal axis. To maximize bead-cell interactions in the lysis chamber, the CD was spun forward and backwards around this axis, using high acceleration for 5 to 7 min. Investigation on inter-particle forces (friction and collision) identified the following parameters; bead density, angular velocity, acceleration rate, and solid volume fraction as having the most significant contribution to cell lysis. Cell disruption efficiency was verified either through direct microscopic viewing or measurement of the DNA concentration after cell lysing. Lysis efficiency relative to a conventional lysis protocol was approximately 65%. In the long term, this work is geared towards CD based sample-to-answer nucleic acid analysis which will include cell lysis, DNA purification, DNA amplification, and DNA hybridization detection. 相似文献
87.
Jung SY Lim SM Albertorio F Kim G Gurau MC Yang RD Holden MA Cremer PS 《Journal of the American Chemical Society》2003,125(42):12782-12786
The molecular level details of the displacement of surface adsorbed fibrinogen from silica substrates were studied by atomic force microscopy, immunochemical assays, fluorescence microscopy, and vibrational sum frequency spectroscopy. The results showed that human plasma fibrinogen (HPF) can be readily displaced from the interface by other plasma proteins near neutral pH because the positively charged alpha C domains on HPF sit between the rest of the macromolecule and the underlying surface. The alpha C domains make weak electrostatic contact with the substrate, which is manifest by a high degree of alignment of Lys and Arg residues. Upon cycling through acidic pH, however, the alpha C domains are irreversibly removed from this position and the rest of the macromolecule is free to engage in stronger hydrogen bonding, van der Waals, and hydrophobic interactions with the surface. This results in a 170-fold decrease in the rate at which HPF can be displaced from the interface by other proteins in human plasma. 相似文献
88.
Beaudoin E Gourier C Hiorns RC François J 《Journal of colloid and interface science》2002,251(2):398-408
Hydrophobically modified poly(ethylene oxide), HMPEO, was studied in concentrated salt solutions. The influence of salts was compared to the effect of temperature on poly(ethylene oxide), PEO. As expected, the addition of monovalent cations (Na(+), K(+)) has the same effect as an increase in temperature in agreement with the thermodynamic properties of PEO: a decrease in solubility, micelle size, and viscosity was observed. Moreover, the intensity of neutron scattering peaks (characteristic of the semi-dilute solutions of these associative polymers) increases due to the collapse of PEO coronae in micelles. Very peculiar behavior was observed in the presence of divalent cations (Ca(2+), Mg(2+)): larger micelle aggregates and higher viscosities, relaxation times, and activation energies were observed by dynamic rheology. This behavior is attributed to interactions between divalent cations and oxygen in PEO backbones close to the micelle core, which may reinforce intermicellar bridges. 相似文献
89.
Cardinali F Mamlouk H Rio Y Armaroli N Nierengarten JF 《Chemical communications (Cambridge, England)》2004,(14):1582-1583
A multicomponent array made of a bis-copper(I) helicate core and two peripheral fullerene subunits has been prepared and electron transfer from the photoexcited Cu(I)-complexed unit to C60 occurs. 相似文献
90.
Jensen TR Breyfogle LE Hillmyer MA Tolman WB 《Chemical communications (Cambridge, England)》2004,(21):2504-2505
A new Zn alkoxide catalyst supported by an N-heterocyclic carbene rapidly polymerizes D,L-lactide (D,L-LA) to heterotactic enriched poly(lactide)(PLA), while the free carbene and analogs instead yield highly isotactic enriched PLA. 相似文献